JP6843758B2 - Aryl compounds and polymers and methods for producing and using them - Google Patents

Description

Cross-reference of related applications

This application is in the interests and priority of US Provisional Application Nos. 62 / 135,692 filed on March 19, 2015 and US Provisional Application No. 62 / 182,351 filed on June 19, 2015. Claim rights, each of which is incorporated herein by reference in its entirety.

The present disclosure relates to aryl compounds and polymeric aryl compounds and methods of producing and using them.

Peropylene compounds as large polycyclic aromatic hydrocarbons (LPAHs) have structural features that impart unique photophysical properties to such compounds. However, since it is difficult to prepare and derivatize such compounds, their usefulness has not yet been utilized in various applications. Perylene diimide derivatives have a similar core as a perylene compound, which has been prepared and analyzed. Chiral conjugated molecules are a type of research of interest because they are useful in areas such as polarized photoluminescence and enantioselective sensing. There are methods for introducing chirality into conjugated materials, including the addition of chiral auxiliary or the synthesis of twisted LPAHs that cause axial chirality as seen in helicene. For example, axial asymmetry has been observed for twisted perylenemidi derivatives in which substituents at recessed positions twist the PAHs to relieve steric strain. This is seen even if the substituent is hydrogen, albeit with a low barrier to enantioma inversion. However, in the art, there is a need for a method of introducing chirality into a peropylene molecule.

Other aromatic rings containing peropylene cores, such as graphene, organics consisting of two-dimensional monolayers of sp2-hybridized carbon atoms, are also important. Graphene has been shown to have interesting electronic, temperature, mechanical, and optical properties. The properties of the graphene material can be changed by changing the size and shape of the graphene sheet. These materials are important for device applications such as thin film transistors (TFTs) and field effect transistors (FETs) because of their interesting electronic properties. Specifically, graphene is a zero bandgap semiconductor, while graphene nanoribbons have a persistent bandgap, which makes graphene nanoribbons a useful material in thin film transistors (TFTs). One particular region of importance is to cut the graphene sheet into strips known as graphene nanoribbons that have different properties than graphene. The approach of exfoliating graphite to produce graphene and then cutting the graphene is known as the "top-down" approach. This method causes a mixture of graphene nanoribbons of different sizes and shapes, and the solubility of the product is typically low, making it difficult to process the material for device applications. Also, the harsh conditions used to produce graphene nanoribbons using a "top-down" approach (lithographic patterning of graphene or unzipping of carbon nanotubes) can cause graphene oxide nanoribbons, which can affect the electronic properties of the material. It has a significant effect. Therefore, there is a need in the art for manufacturing graphene nanoribbons that can address these shortcomings.

FIG. 5 is a view of the propylene core (100), the chiral propylene core (102), and the top surfaces (104 and 106, respectively) and sides (108 and 110, respectively) of those cores. It is a figure of the rotating coordinate system overhauser effect spectrum (ROESY spectrum) of the typical intermediate compound disclosed in this specification. It is a figure of the NOESY spectrum of the representative intermediate compound disclosed in this specification. It is a figure of the combination of the UV-Vis spectrum and the fluorescence spectrum of the typical intermediates and compounds disclosed herein. It is a figure of the combination of the UV-Vis spectrum and the fluorescence spectrum of the typical intermediates and compounds disclosed herein. It is a figure of the combination HPLC trace of the typical intermediates disclosed herein. It is a calculated image of Molecular Force Field 94 for a representative compound disclosed herein. It is a figure of the representative intermediate compound disclosed in this specification. It is a figure of the combination of the UV-Vis spectrum and the fluorescence spectrum of the typical compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of the representative intermediate compound disclosed in this specification. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds disclosed herein. ^{It is a figure of 1} H-NMR spectrum of the representative intermediate compound disclosed in this specification. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds disclosed herein. ^{It is a figure of 1} H-NMR spectrum of the representative intermediate compound disclosed in this specification. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds disclosed herein. ^{It is a figure of 1} H-NMR spectrum of a typical boronic acid ester compound disclosed in this specification. ^{It is a figure of the 13} C-NMR spectrum of the typical boronic acid ester compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of a typical boronic acid ester compound disclosed in this specification. ^{It is a figure of the 13} C-NMR spectrum of the typical boronic acid ester compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of a typical boronic acid ester compound disclosed in this specification. ^{It is a figure of the 13} C-NMR spectrum of the typical boronic acid ester compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of the representative peropylene precursor compound disclosed in this specification. It is a figure of ^{the 13} C-NMR spectrum of the representative peropylene precursor compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of the typical peropylene compound disclosed in the present invention. It is a figure of ^{the 13} C-NMR spectrum of the representative peropylene compound disclosed in the specification. ^{It is a figure of 1} H-NMR spectrum of the representative peropylene precursor compound disclosed in this specification. It is a figure of ^{the 13} C-NMR spectrum of the representative peropylene precursor compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of the representative intermediate compound disclosed in this specification. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds disclosed herein. ^{It is a figure of 1} H-NMR spectrum of the representative intermediate compound disclosed in this specification. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds disclosed herein. ^{It is a figure of 1} H-NMR spectrum of the representative intermediate compound disclosed in this specification. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds disclosed herein. ^{It is a figure of 1} H-NMR spectrum of the typical chiral peropylene compound disclosed in this specification. ^{It is a figure of the 13} C-NMR spectrum of the typical chiral peropylene compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of the typical chiral peropylene compound disclosed in this specification. ^{It is a figure of the 13} C-NMR spectrum of the typical chiral peropylene compound disclosed in this specification. ^{It is a figure of 1} H-NMR spectrum of the typical chiral peropylene compound disclosed in this specification. ^{It is a figure of the 13} C-NMR spectrum of the typical chiral peropylene compound disclosed in this specification. It is a figure of the gel permeation chromatogram of an exemplary compound embodiment. FIG. 5 is a diagram of a combined Raman spectrum showing the spectrum of an exemplary compound embodiment, the spectrum of the compound after baseline correction, and the baseline spectrum. FIG. 5 is a diagram of a combined Raman spectrum showing the spectrum of an exemplary compound embodiment, the spectrum of the compound after baseline correction, and the baseline spectrum. It is a figure of the combined UV-Vis spectrum which shows the spectrum of the exemplary peropyrene polymer disclosed herein and the polymer synthesized using various different acids. ^{It is a figure of 1} H-NMR spectrum of a typical intermediate compound used in the method disclosed herein. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds used in the methods disclosed herein. ^{It is a figure of 1} H-NMR spectrum of a typical intermediate compound used in the method disclosed herein. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds used in the methods disclosed herein. ^{It is a figure of 1} H-NMR spectrum of a typical intermediate compound used in the method disclosed herein. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds used in the methods disclosed herein. ^{It is a figure of 1} H-NMR spectrum of a typical intermediate compound used in the method disclosed herein. FIG. 5 is a diagram ^{of 13} C-NMR spectra of representative intermediate compounds used in the methods disclosed herein. ^{It is a figure of 1} H-NMR spectrum of a typical boronic acid ester compound used in the method disclosed in this specification. ^{It is a figure of the 13} C-NMR spectrum of a typical boronic acid ester compound used in the method disclosed herein. ^{FIG. 5 is a 1} H-NMR spectrum of a representative polymer precursor used in the methods disclosed herein. FIG. 5 is a diagram ^{of 13} C-NMR spectra of typical polymer precursors used in the methods disclosed herein. FIG. 5 is a diagram of a ^{combined 1 H-NMR spectrum showing the results of 1} H-NMR analysis for an intermediate embodiment, a pyrene embodiment, a polymer embodiment, and a polymer embodiment. FIG. 5 is a diagram of a ^{combined 13 C-NMR spectrum showing the results of 13} C-NMR analysis for the intermediate embodiment, the pyrene embodiment, the polymer embodiment, and the polymer embodiment of FIG. FIG. 5 is a combined FTIR full spectrum diagram showing spectra obtained by IR analysis of a polymer embodiment and a polymer embodiment formed using methyl sulfonic acid (MSA). It is a figure of the combined FTIR full spectrum which shows the spectrum obtained by the IR analysis of the polymer embodiment and the polymer embodiment formed using TFA-TfOH. It is an image of a polymer embodiment and is a TEM image of a polymer embodiment. FIG. 3 is a TEM image using _{RuO 4} staining showing the curved region of the polymer embodiment. It is a TEM enlarged image of a polymer sheet showing a long linear strand in which nanoribbons are assembled. It is an XRD image of a polymer embodiment which shows the crystallinity of a polymer embodiment. It is a high resolution TEM image of a polymer embodiment on a copper grid coated with lace-like carbon. It is a TEM image showing a thin plate of aggregated nanoribbons obtained by using high-contrast RuO _{4 staining.} It is a TEM image showing a bundle of short nanoribbons with a length of about 30 nm. It is an exemplary STM image and space-filled image of an exemplary nanostructured compound. It is a figure of ^{the combination 1} H-NMR spectrum of a pyrene intermediate and a compound disclosed in this specification. FIG. 5 is a diagram of a polymer and polymer product combination ^{1 H-NMR spectrum disclosed herein.} FIG. 5 is a diagram of a polymer and polymer product combination ^{1 H-NMR spectrum disclosed herein.} FIG. 5 is a diagram of a ^{combination 1} H-NMR spectrum of a representative polymer and a representative polymer product disclosed herein. It is a figure of the combination IR spectrum of a polymer and a polymer product disclosed herein. It is a figure of the STM image of the compound disclosed in this specification. It is an image which shows the torsional property of the nanostructure compound disclosed in this specification. It is a figure of ^{the combination 1} H-NMR spectrum of the compound disclosed in this specification. It is a figure of ^{the combination 1} H-NMR spectrum of the compound disclosed in this specification. 49A is a diagram of spectra obtained from the representative compounds disclosed herein, and is a diagram of a combination normalized UV-vis absorption spectrum. 49B is a combination normalization 50A is a diagram of STM images of representative compounds at the HOPG / TCB interface, I = 0.4nA, V = 300mV. 50B is a diagram of STM images of representative compounds at the HOPG / TCB interface, I = 0.3nA, V = 250mV. It is an X-ray image of a typical compound. It is an X-ray image of a typical compound. It is an X-ray image of a typical compound. It is an X-ray image of a typical compound.

I. Terminology Descriptions of the following terms are provided to better describe the disclosure and guide those skilled in the art in practicing the disclosure. As used herein, "comprising" means "including," in the singular forms "one (a),""one(an)," and "the." Includes multiple referents, unless the context clearly means something else. The term "or" refers to a single element or a combination of two or more of the alternative elements referred to, unless the context clearly means something else.

For convenience of presentation, some steps of the disclosure method are described in a particular continuous order, but this description scheme is arranged in a particular order unless required by the particular language described below. Please understand that it includes replacement. For example, the steps listed in sequence can be rearranged or performed simultaneously in some cases. In addition, the description may describe the method of disclosure using terms such as "produce" or "provide". These terms are a high degree of abstraction of the actual steps performed. The actual steps corresponding to these terms will vary depending on the particular practice and will be readily recognized by those skilled in the art.

Unless otherwise stated, all terminology and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Methods and compounds similar to or equivalent to those described herein can be used in the practices or tests of the present disclosure, but suitable methods and compounds are described below. Compounds, methods, and examples are merely exemplary and are not intended to be limiting unless otherwise specified. Other features of the disclosure will be revealed by the following detailed description and claims.

Unless otherwise specified, it is understood that all numbers used in the specification or claims for component weight, molecular weight, percentage, temperature, time, etc. are modified by the term "about". I want to be. Therefore, unless otherwise specified implicitly or explicitly, the numerical parameters described are approximations that may depend on the desired characteristics sought and / or detection limits under standard test conditions / methods. When making a direct and explicit distinction between the prior art and the embodiments discussed, the numbers in the embodiments are not approximations unless the word "about" is mentioned.

Moreover, not all alternatives described herein are equivalent. The following terms and definitions are provided. The term for a functional group includes a ^Ra group, which is not part of the defined functional group but indicates how the functional group attaches to the compound to which it is attached.

Aliphatic: A hydrocarbon or a group having at least 1 to 50 carbon atoms such as 1 to 25 carbon atoms or 1 to 10 carbon atoms, and an alkane (or alkyl), alkene ( Or alkenyl), alkyne (or alkynyl), its cyclic form, further including linear and branched sequences, including all steric and positional isomers.

Alkyl: A saturated monovalent hydrocarbon having at least 1 to 50 carbon atoms, such as 1 to 25 carbon atoms or 1 to 10 carbon atoms, the saturated monovalent hydrocarbon being the parent compound. It can be obtained by removing one hydrogen atom from one carbon atom (eg, alkane). Alkyl groups can be branched, linear, or cyclic (eg, cycloalkyl).

Alkenyl: An unsaturated monovalent hydrocarbon having at least 2 to 50 carbon atoms, such as 2 to 25 carbon atoms or 2 to 10 carbon atoms, and at least one carbon-carbon double bond. Therefore, the unsaturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of the parent arcene. The alkenyl group can be branched, linear, cyclic (eg cycloalkenyl), cis, or trans (eg E or Z).

Alkinyl: An unsaturated monovalent hydrocarbon having at least 2 to 50 carbon atoms, such as 2 to 25 carbon atoms or 2 to 10 carbon atoms, and at least one carbon-carbon triple bond. Therefore, the unsaturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of the parent alkin. The alkynyl group can be branched, linear, or cyclic (eg, cycloalkynyl).

Alkoxy: -O-alkyl, having exemplary embodiments including, but not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy. , -O-alkoxy, or -O-alkynyl.

Ambient temperature: A temperature in the range of 16 ° C to 26 ° C, such as 19 ° C to 25 ° C or 20 ° C to 25 ° C.

Amines: -NR ^b R ^c , R ^b and R ^c are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, heteroaryl, and combinations thereof.

Aryl: An aromatic carbocyclic group having a monocyclic or polycondensed ring and containing at least 5 to 15 carbon atoms such as 5 to 10 carbon atoms, and the fused ring is an attachment point. May or may not be aromatic if is mediated by an atom of an aromatic carbocyclic group.

Diyne: An aryl compound containing two alkyne groups, typically said alkyne group is placed on the aryl ring such that at least one carbon atom of the aryl compound is located between the two alkyne groups. ..

Electron accepting group: A functional group capable of receiving an electron density from a ring directly attached to it by inducible electron attraction or the like.

Electron donating group: A functional group capable of donating at least a part of its electron density to a ring directly attached by resonance or the like.

Aliphatic group: An aliphatic group in which one or more hydrogen atoms such as 1 to 10 hydrogen atoms are independently substituted with halogen atoms such as fluorine, bromine, chlorine, or iodine.

Haloalkyl: An alkyl group in which one or more hydrogen atoms, such as 10 to 10 hydrogen atoms, are independently substituted with halogen atoms, such as fluorine, bromine, chlorine, or iodine. _{In an independent embodiment, the haloalkyl can be three} CX groups, each of which can be independently selected from fluorine, bromine, chlorine, or iodine.

Halogen-metal exchange: A reaction in which a bond between a halogen atom and a carbon atom is converted into a bond between a metal atom and a carbon atom using the metal-containing compounds described herein.

Heteroatoms: At least one, but not limited to, 1 to 15 heteroatoms or 1 to 5 heteroatoms that can be selected from oxygen, nitrogen, sulfur, selenium, phosphorus, and their oxidants. Heteroatom to 20 heteroatoms in the group.

Heteroalkyl / Heteroalkenyl / Heteroalkynyl: 1 to 15 heteroatoms or 1 to 5 heteros that can be selected from, but not limited to, oxygen, nitrogen, sulfur, selenium, phosphorus, and their oxidants. An alkyl, alkenyl, or alkynyl group (which can be branched, linear, or cyclic) containing at least one heteroatom to 20 heteroatoms, such as an atom, within the group.

Heteroaryl: At least one heteroatom to six heteroatoms, including, but not limited to, oxygen, nitrogen, sulfur, selenium, phosphorus, and 1 to 4 heteroatoms that can be selected from their oxidants. Aryl group containing in the ring. Such a heteroaryl group may have a monocyclic or polycondensed ring, which may or may not be aromatic if the attachment point is via an atom of an aromatic heteroaryl group. It may or may not contain atoms.

Metal-Containing Compounds: The metal-containing compound can be any compound, including metals, which can undergo a halogen-metal exchange reaction with the compounds or compound precursors described herein. Suitable metal-containing compounds include, but are not limited to, Mg, Li, and the like.

It will be appreciated by those skilled in the art that the definitions provided above are not intended to include unacceptable substitution patterns (eg, methyl substituted with 5 different groups). Such unacceptable substitution patterns are readily recognized by those skilled in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise specified herein.

II. Overview The methods disclosed herein address the disadvantages of conventional methods for producing benzene-containing compounds such as pyrene compounds, peropylene-based compounds, and polymer structures such as nanostructures (eg, nanoribbons). In particular, high yield alkyne aromatic cyclization reactions that provide polycyclic aromatic hydrocarbons (PAHs) such as pyrene and peropylene are used. In contrast to conventional peropylene synthesis, the methods disclosed herein are efficient, high yielding and do not require harsh reaction conditions. In one embodiment, efficient double cyclization of Bronsted acid-catalyzed 2,6-dialkynylbiphenyl derivatives can be used to prepare 4,10-disubstituted pyrene derivatives. An exemplary peropylene is shown in FIG. 1, which provides various views of the compound.

Since the discovery of graphene, research has been conducted on related materials, namely graphene nanoribbons. The harsh conditions used to produce graphene nanoribbons using a "top-down" approach (lithographic patterning of graphene or unzipping of carbon nanotubes) can cause graphene oxide nanoribbons, which significantly affects the electronic properties of the material. To do. Also, this top-down method typically produces impure graphene nanoribbons as a mixture of low solubility and different sizes and shapes, which makes it difficult to process the material for device applications. Other conventional methods allow the formation of nanoribbons using solution-mediated or surface-assisted polymerization of linear polyphenylene molecular precursors followed by dehydrogenation. Several "bottom-up" approaches for graphene nanoribbons have been reported, which rely on the formation of aryloxide bonds (eg, the Scholl reaction) for important CC bond formation reactions, which are required for these methods. Severe conditions significantly limit the functionality that can be incorporated into graphene nanoribbons, thus limiting the ability to adjust properties through substitutions. Also, the conventional bottom-up method produces only a limited amount of material.

In some embodiments, it is possible to produce twisted axial chirality peropylene derivatives using the methods disclosed herein. It is also possible to modify this method to produce narrow polymer nanostructures, such as nanoribbons (about 0.5 nm wide), which are highly soluble in some common organic solvents. The methods disclosed herein allow better control of the size, shape, and functionalization of nanostructures (eg, nanoribbons), which leads to improved solubility and material properties. In the embodiments disclosed herein, a highly soluble, very narrow armchair end polymer structure (eg, nanoribbon) is subjected to a Bronsted acid-induced alkyne aromatic cyclization that does not require a dehydrogenation cyclization reaction step. It can be manufactured using a reaction strategy. These soluble, narrow polymer structures can have significant value in terms of metallicity relative to semiconductivity in many nano-semiconductor applications (eg, FET applications). In some embodiments, the polymer compound (eg, a nanoribbon such as a graphene nanoribbon) is a gel permeation chromatography (GPC) (eg, FIG. 25), a high performance liquid chromatography (HPLC) (eg, FIG. 6) nuclear magnetic resonance. (NMR), infrared spectroscopy (eg, FIGS. 37 and 38), Raman spectroscopy (eg, FIGS. 26 and 27), ultraviolet-visible (UV-vis) spectroscopy, fluorescence spectroscopy (eg, FIGS. 4, 5, 5, 9, 49A, and 49B), as well as transmission electron microscopy (TEM) (eg, FIGS. 39A-39G) and scanning tunnel microscope (STM) (eg, FIGS. 40, 50A and 50B).

III. Compounds In certain disclosure embodiments, compounds having the following formulas can be prepared according to the methods disclosed herein.

Equation 1

Equation 2

Equation 3

Equation 4

Equation 5

It relates formula 1-5, each R ¹ parts, can be selected to control the chemical and / or electrochemical properties of enhanced solubility and / or compounds. In some embodiments, each R ¹ can be independently selected from hydrogen, aliphatic, aryl, heteroaliphatic, or heteroaryl; each R ^a is independently aryl; aliphatic, alkoxy. , Aryl, amine, thioether, haloalkyl, nitro, halo, silyl, alicyclic, and aryl substituted with one or more functional groups selected from aryl, etc .; or can be selected from electron donating groups. Each n can be independently 1, 2, or 3; m can be 0 to 1000 or more. Exemplary electron donating groups include, but are not limited to, alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, silyloxy, and heteroaryl (eg, thiophene). Such groups of the aryl ring substituted with one or more functional groups are located in meta, ortho, para, or a combination thereof with respect to the position to which ^{Ra is attached.} A moiety capable of R ¹ controls the chemical and / or electrochemical properties of the replaced or modified by a compound, and in yet another embodiment, the electron donating each R ¹ is as described above for R ^a It is possible to select from the groups; R ¹ can also be selected from the electron-withdrawing groups (CN, halogen, nitro, ester, etc.).

Illustrative compounds that fit Formulas 1-3 are provided below.

In some embodiments, the methods disclosed herein can be used to generate nanostructures, such as nanoribbons, having formula 6 or 7.

Equation 6

Equation 7

For formulas 6 and 7, each X can be independently selected from hydrogen or terminal functional groups, and m can range from 1 to 1000 or more. Each, or R ¹ , R ^a , and n, can be as described above. In some embodiments, each R ¹ can be independently selected from hydrogen, aliphatic, aryl, heteroaliphatic, or heteroaryl; each R ^a is independently aryl; aliphatic, alkoxy. , Aryl, amine, thioether, haloalkyl, nitro, halo, silyl, alicyclic, and aryl substituted with one or more functional groups selected from aryl, etc .; or can be selected from electron donating groups. Each n can be 1, 2, or 3 independently. Suitable terminal functional groups can be selected from functional groups such as _{-SO 3} CH ₃ , -SO ₃ CF _{3, or halogen.} In some embodiments, ^Ra is an aryl substituted with one or more functional groups, the one or more functional groups being meta, ortho, para, relative to the position to which the ^{Ra group is attached.} Or it can be located in a combination thereof. In some embodiments, m can range from 2 to 500 or greater, or 3 to 100 or greater, or 4 to 50 or greater. In an exemplary embodiment, m is in the range 10-80. Illustrative compounds satisfying formulas 6 and 7 are shown below.

IV. Methods for Producing Compounds Disclosed herein are methods for producing pyrene compounds, peropylene-based compounds, and polymer compounds that satisfy the above formulas.

A method for producing a pyrene compound is described in Scheme 1 below. For Scheme 1, prepare 2,6-bis [(4- “R” -phenyl) ethynyl] biphenyl 104, which then triggers a double cyclization reaction, presumably via monocyclization intermediate 106. 4,10-Diarylpyrene derivative 108 is produced under cyclization conditions using various Bronsted acids.

The results of embodiments using trifluoroacetic acid and different solvent systems and conditions are provided in Table 1. In some embodiments, 104 is treated with 10 equivalents of methanesulfonic acid or p-toluenesulfonic acid for _{1 day in anhydrous CH 2} Cl ₂ at room temperature, after which 108 separately yields 60% or 73%. It was confirmed that high yields such as rate were obtained (see, for example, entries 4 and 5 in Table 1). All results showed that the acid strength had a direct effect on the yield of pyrene. Trifluic acid resulted in rapid (within 5 minutes) formation of pyrene 108 at −40 ° C. without detection of monocyclization 106 in the crude product, 108 was obtained in near quantitative yield (entry 6, entry 6, Table 1). Without being limited to a particular operating principle, it is currently believed that the efficiency and yield of the reaction will improve significantly as the acidity of the Bronsted acid increases.

Scheme 1

In some embodiments, additional pyrene and peropylene-based compounds are prepared using the methods described below. As shown in Scheme 2, starting diyne compound 206 can be prepared using the method steps shown below. In some embodiments, the starting material 200 is halogenated to provide the halogenated compound 202. The reaction of the halogenated compound 202 with an appropriate reagent that triggers the aromatic substitution reaction (eg, a reagent suitable for a radical aromatic substitution reaction) provides compound 204, which is then cross-cuped with two alkyne moieties. It is possible to ring to provide the reagent 206.

Scheme 2

For Scheme 2, R ¹ can be as described herein; R ² can be an amine (eg, NH ₂ ); X and Y can be independent of each other, I. , Br, F, and Cl can be selected from halogens; each ^Ra group can be independently as described herein. In an exemplary embodiment, R ¹ is hydrogen or alkyl, R ² is NH ₂ , X is I, and Y is Br. An exemplary embodiment of the above method is provided in Scheme 3 below.

Scheme 3

The synthesis shown in Scheme 3 was initiated by iodination of 4-tert-butylaniline 300 to give 4-tert-butyl-2,6-diiodaniline 302, followed by the Sandmeyer reaction to give compound 304. .. Compound 304 was then subjected to a double cross-coupling reaction with an electron-rich alkyne to give 1-bromo-2,6-dialkynyl compound (306).

In some embodiments, the diyne 206 can be converted to a suitable polymer precursor using the boronic acid-based coupling method shown in Scheme 4. In some embodiments, the boronic acid-based coupling contains the diyne 206 to compound 402 (where R ⁵ is B [-OC (R ⁶ ) ₂ C (R ⁶ ) ₂ O-], in the formula. Each R ⁶ is independently selected from hydrogen, aliphatic, or aryl) and involves exposure to boron pinacol esters to produce the polymer precursor 406. In some embodiments, the formation of a boronic acid or boron ester following a halogen-metal exchange reaction with a metal-containing compound can be used to produce compound 400, which is then bromo compound 404. 2,6-Dialkynylbiphenyl derivative 406 is produced by subjecting it to a palladium-based reaction. In yet another embodiment, the 2,6-dialkynylbiphenyl derivative 406 can be directly prepared by coupling the diyne 206 with the boron pinacol ester 402. The diyne 406 can then be cyclized with an acid to form the pyrene product 412. Exemplary acids include, but are not limited to, HCO ₂ CF ₃ , HOSO ₂ CH ₃ , and HOSO ₂ CF ₃ . In some embodiments, incomplete cyclization may provide compound 408, but this product can be avoided by warming the reaction mixture from low temperature (eg, below 0 ° C.) to room temperature.

Scheme 4

With respect to Scheme 4, R ¹ , Y, and Ar are as described above for Scheme 2, respectively; R ⁴ is boronic acid; R ⁵ is a boronic acid ester. In some embodiments, R ⁴ is B (OH) ₂ . In some embodiments, R ⁵ is B [-OC (R ⁶ ) ₂ C (R ⁶ ) ₂ O-], where each R ⁶ is independently selected from hydrogen, aliphatic, or aryl. To. In some exemplary embodiments, R ⁵ is B [-OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O-]. In some embodiments, for the formation of boronic acid esters or boronic acids, compound 206 is exposed to metal-containing compounds (eg, n-BuLi, s-BuLi, and t-BuLi) in a solvent to halogen-. It may include facilitating metal exchange followed by coupling of the boronic acid or boronic acid ester (eg, the boronic acid ester having the above formula). In an exemplary embodiment, a boronic acid ester such as pinacol boronic acid ester is used. The cross-coupling reaction as shown in Scheme 4 may include promoting the coupling of a boronic acid ester compound or a boronic acid compound (eg, Compound 402) with Compound 206 using a palladium-based reagent. In yet some other embodiments, the cross-coupling may include the use of palladium-based reagents to promote the binding of compound 400 to a halogenated coupling partner such as compound 404. Suitable palladium-based reagents include, but are not limited to, Pd (PPh ₃ ) ₄ , Pd (OAc) ₂ , PdCl ₂ , Buchwald palladium reagents (eg XPhos Pd, SPhos Pd, RuPhos Pd, and CPhos Pd. Etc.), or Hartwig palladium reagents (eg, bis (tris (2-tolyl) phosphine) palladium Pd [(o-tol) ₃ P] ₂ , and QPhos Pd, etc.). An exemplary embodiment of the method shown in Scheme 4 is shown in Scheme 5.

In the exemplary embodiment shown in Scheme 5, Suzuki cross-coupling conditions were used. In some embodiments, the cross-coupling reaction between 306a and 4-tert-butylphenylboronic acid pinacol ester 502 formed trace amounts of the desired 2,6-diylbiphenyl product 506. In some embodiments, different coupling partners were evaluated by converting compound 306a to boronic acid pinacol ester 500, but successful cross-coupling with 4-tert-butylbromobenzene 504 resulted in 2, 6-Diynylbiphenyl 506 was obtained in moderate yield. The synthesis of substrate 506 makes it possible to determine whether double cyclization is feasible and the legio selectivity of cyclization. In some embodiments, the double cyclization of compound 506 was accompanied by the use of a catalytic amount of methanesulfonic acid at 0 ° C. Although it is possible to form the monocyclized phenanthrene product 508, in some embodiments the conversion may be slow. Increasing the amount of acid can significantly improve the reaction speed. With 2-3 equivalents of acid, the reaction can be completed within 10 minutes, which is monocyclic in near quantitative yield without detection of the 5-membered legio isomer product 510. It resulted in the exclusive formation of the phenanthrene product 508. The reaction was warmed to room temperature to result in double cyclization, providing pyrene product 512. The 5-membered ring products 510 and 514 were not detected in most embodiments, but could potentially be isolated. In some embodiments, the coupling partner can be adjusted by converting compound 306a to boronic acid pinacol ester with 502 and successful cross-coupling with 1,4-diiodobenzene. Thus, in moderate yields, 2', 2'', 6', 6''-tetrinylterphenyl derivative 506 was obtained.

Scheme 5

In yet another embodiment, the peropylene-based compound can be formed using the method shown in Scheme 6. Similar to Schemes 4 and 5, it is possible to prepare compound 602 using a halide-metal exchange reaction and a boronic acid ester (or boronic acid) coupling reaction sequence. Compound 400 can be cross-coupled with a di-halogenated aryl compound such as Compound 600 shown in Scheme 6. This cross-coupling provides a terphenyl derivative 602. Treatment of the terphenyl derivative 602 with an acid at the first temperature gives intermediate 604. Treatment of Intermediate 604 with another acid at a second temperature gives fully cyclized peropylene compound 606. In some embodiments, the use of the following acid-catalyzed reactions is used to convert Intermediate 604 to the desired peropylene product.

Scheme 6

An exemplary embodiment of the method shown in Scheme 6 is shown in Scheme 7 below. In some embodiments, dicyclization intermediate 704b was obtained in 97% yield with the addition of TFA at room temperature. This was proved by NMR and X-ray crystal analysis. After screening for various other Bronsted acids, the tetracyclization product 706b (and other compounds such as 706a, 706c, and 706d) was used with 2 equivalents of trifluic acid (TfOH) at -40 ° C. It was revealed that it can be formed cleanly and rapidly without any acid-degrading compound. In some embodiments, the dicyclization / quaternization procedure can be performed as a "one-pot" process. In some embodiments, the one-pot process is a single 706a and 706c in yields of 38% and 45% from the 2', 2'', 6', 6''-tetrinyl terphenyl derivatives 702a and 702c, respectively. It is possible to cause separation (Scheme 7).

Scheme 7

In some embodiments, the progression of the reaction described in Schemes 6 and 7 above can be observed using thin layer chromatography. The intermediates obtained from such reactions can be characterized using a variety of techniques, which are disclosed herein. Such an intermediate is shown in Scheme 8. By avoiding some of the intermediates shown below using the methods disclosed herein, the control of the reaction products provided by the methods disclosed herein is shown and their use on a commercial scale. It is possible to prove the feasibility of.

Scheme 8

The dicyclization intermediate produced using the above method can be further converted to a peropylene product using an acid-catalyzed cyclization reaction. In some embodiments, an acid such as _{CF 3} SO ₃ H or a pKa _{that is substantially similar to CF 3} SO _{3 H, such as trifluimide acid (HNTf 2} ), methane sulfonic acid, benzene sulfonic acid, and p-toluene sulfonic acid. It is possible to cyclize the bicyclization intermediate to a peropylene-based compound using any Bronsted acid having. In some embodiments, low temperatures (eg, greater than -100 ° C to less than 25 ° C or greater than -50 ° C to less than 10 ° C or greater than -40 ° C to less than 0 ° C, etc. It can be used during acid-catalyzed conversion to peropylene-based compounds.

In certain disclosed embodiments, the reaction pathways shown in Scheme 8 can be clearly observed by thin layer chromatography and intermediates characterized by the various techniques described herein. Scheme 8 shows various possible intermediates. The speed of the first two cyclizations between rings A and B and B and C may be due to the flexibility of the substrate and the free rotation of the terphenylbenzene ring, which is the newly formed rings D and E. Allows good orbital overlap of carbon-carbon bonds. Once the ring D is formed and a flattened phenanthryl moiety is formed, the second alkyne cyclization between the rings A and B becomes more difficult due to poor orbital overlap (Scheme 8). Free rotation between rings B and C is still possible, the second cyclization is rapid, and it is also possible to produce ring E, which provides intermediate 704. No formation of intermediate 712 was observed. Intermediate 704 can be isolated and its structure can be confirmed using X-ray crystallography. Compound 704 is axially asymmetric. From the structure of 704, third and fourth cyclizations that produce rings F and G originating in opposite directions, which produce axially asymmetric enantioma 706 in contrast to meso compound 718, may be preferred. Compound 716 undergoes a fourth cyclization to rapidly provide the quaternization product 706. Additional exemplary methods of producing the compounds disclosed herein are provided in Schemes 9-14.

Scheme 9
Scheme 10
Scheme 11
Scheme 12
Scheme 12 (continued)
Scheme 13A
Scheme 13B
Scheme 14

Using the methods described in Schemes 13 and 14, it is possible to extend the aromatic ring system from the non-K region without changing the width of the condensed aromatic skeleton. This is a feature that has not been achieved by conventional methods. With respect to Scheme 14, it is possible to carry out a dicyclization reaction of compound 1402 to produce peropylene-based compound 1406. As shown in Scheme 14, compound 1402 was isolated in 76% yield by Suzuki coupling reaction of 2,6-dialkynebenzenepinacol boronate 1400 and 2-bromopyrene 1300a. Compound 1402 provided the monoaromatic cyclization product 1404 almost quantitatively in the presence of excess trifluoroacetic acid (TFA) at room temperature. ^{As can be seen from 1} H NMR of compound 1404, the protons in the recessed position provide a sharp singlet signal at about 11.12 ppm (H ₁ , Scheme 14). At this time, but not limited to a particular theory, this extreme anti-shielding is a flattening phenanthryl formed in compound 1404 after the first cyclization that occurs _{in H 1 of the remaining alkyne anti-shielding zone.} It is believed to be due to its shape. In some embodiments, compound 1406 was not observed in the presence of TFA at room temperature, even after a long reaction time. No change was seen in the reactants after adding trifluic acid (TfOH) (1 eq) to the solution at −78 ° C., but warming the reactants to −40 ° C. completed the second alkyne cyclization immediately. , Brought peropylene 1406.

In certain disclosure embodiments, it is possible to enantioselectively produce the peropylene-based products disclosed herein. As shown herein, the formation of dicyclized intermediates disclosed herein is rapid, and these intermediates are also axially asymmetric. Therefore, the invention of the present disclosure has discovered that it is possible to generate a chiral peropylene-based compound by inducing double cyclization using a weak chiral Bronsted acid.

In additional embodiments, schemes 1-8 are modified using and / or modified as described above to produce long polymeric peropyrene-containing products, such as nanostructures (eg, graphene nanostructures or graphene-like nanostructures). It is possible to do. In some embodiments, it is possible to obtain compound 206 using a method that replaces the method described in Scheme 2. For example, it is possible to convert the starting material 1500 to triazene compound 1502 and then perform selective double-palladium-based cross-coupling to give dialkynyl triazene 1504. Conversion of dialkynyltriase 1504 to intermediate 206 was achieved by treating dialkynyltriazene 1504 with an alkyl halide. The halogenated intermediate 206 was treated with BuLi for lithium-halogen exchange, trimethoxyborane was added and prepared under acidic conditions to give boronic acid 1506 in good yield. The conversion of boronic acid 1506 to pinacol ester 1508 can be carried out with a suitable diol compound.

Scheme 15

With respect to Scheme 15, R ¹ , R ² , X, Y, and ^Ra , respectively, can be as described herein. In some embodiments, R ¹ can be a halogen selected from Br, I, F, or Cl, or OTf. In some embodiments, each R ³ can be independently selected from hydrogen, aliphatic, or aryl; R ⁴ is a boronic acid; R ⁵ is a boronic acid ester. In some embodiments, R ¹ is Br. In some embodiments, R ³ is selected from alkyl, alkenyl, alkynyl, or aryl. In some embodiments, R ⁴ is B (OH) ₂ . In some embodiments, R ⁵ is B [-OC (R ⁶ ) ₂ C (R ⁶ ) ₂ O-], and each R ^{6 in} the equation is independently selected from hydrogen, aliphatic, or aryl. Will be done. In an exemplary embodiment, R ³ can be selected from methyl, ethyl, propyl, butyl, pentyl and the like. In an exemplary embodiment, R ⁵ is B [-OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O-]. An exemplary embodiment of the method shown in Scheme 15 is provided in Scheme 16 below.

Scheme 16

For the embodiment shown in Scheme 16, synthesis of compound 1610 was initiated by conversion of aniline 1600 to triazene compound 1602, followed by selective double sonogashira cross-coupling to give dialkynyl triazene 1604. Conversion of dialkynyltriase 1604 to bromoiododialkynylbenzene 1604 was achieved by treating dialkynyltriase 1604 with methyl iodide. Bromoiodoalkynylbenzene 1606 was treated with BuLi for lithium-halogen exchange, trimethoxyborane was added and prepared under acidic conditions to give boronic acid 1608 in good yield. The conversion of boronic acid 1608 to boronic acid ester 1610 was done in excellent yield.

The pinacol boronic acid ester (or boronic acid) intermediate disclosed in Schemes 15 and 16 above was polymerized to give the intermediate polymer product, which was then converted to the nanostructured compounds shown in Schemes 17A and 17B below. It is possible to do. For example, as shown in Schemes 17A and 17B, it is possible to convert Intermediate 400 to Polymer Intermediate 1700 using a palladium coupling reaction. It is possible to analyze the polymer 1700 using gel permeation chromatography to determine the polydispersity index (PDI). Exposure of the polymer intermediate 1700 to an acid makes it possible to obtain the nanostructured compound 1702. An exemplary method is shown in FIG. 17B.

Scheme 17A

Scheme 17B

Illustrative embodiments of the methods shown in Schemes 17A and 17B are shown in Schemes 18A and 18B below. As shown in Schemes 18A and 18B, pinacol boronic acid ester 700 is subjected to Suzuki polymerization conditions to obtain an alkynyl-substituted poly (p-phenylene) polymer 1800 (where Ar is phenyl). When polymer 1800 was analyzed using gel permeation chromatography to determine the polydispersity index, some embodiments had PDIs of 1.87 (in toluene) and 1.39 (in THF). Alkyne cyclization was successful with trifluoroacetic acid and trifluic acid to give polymer 1802 (where Ar is phenyl in the formula). Conversion of polymer 1800 to polymer 1802 was ^{confirmed by 1} H NMR, ¹³ C NMR, IR, and Raman spectroscopy. Additional embodiments are shown in Scheme 18B, where different terminal groups are used to terminate the polymer.

Scheme 18A

Scheme 18B

In some embodiments, the choice of reaction solvent (eg, toluene vs. THF) can affect the difference in molecular weight obtained after polymerization. In some embodiments, it can be achieved with a polar solvent such as THF, and the high molecular weight is achieved with THF (see Table 2 below). In some embodiments, a complete aromatic cyclization reaction was observed after 24 hours with excess TFA at room temperature. At this time, although not limited to a particular operating theory, this higher reactivity is believed to be due to the increased flexibility of the polymer and the partially cyclized intermediate. In partially cyclized intermediates derived from 1800 and even flexible systems such as 1802 itself, the "twist" function allows for better orbital overlap, facilitating the aromatic cyclization reaction. (Fig. 47). Significant cyclization of 1800 ^{was observed by 1} H NMR, but in some embodiments the reaction mixture was cooled to −40 ° C. and completed by the addition of a few drops (eg 1-10 drops) of trifluic acid. It is possible to achieve cyclization. The average length of 1800 is estimated to be about 6 nm (toluene) and 20 nm (THF) based on the _{isolated 1800 M w.} There was no change in the molecular weight dispersion of 1802, indicating that no intermolecular reaction occurred during the aromatic cyclization reaction.

_{With respect to Table 2, M w} and M _n were determined by SEC analysis of polymer precursor compounds such as compound 1800 obtained after polymerization (eluting agent: THF). M _w and M _n are the results based on the PS standard calibration, respectively. The PDI value was calculated by _{M w} / M _n. Entry 2 represents the results obtained by analyzing a TFA-promoted polymer using a polymer derived from Entry 1 as a precursor. Entry 4 is an MSA-promoted polymer using the Entry 3 polymer as a precursor. Entry 5 is a TFA-TfOH-promoted polymer using the Entry 4 polymer as a precursor.

In some embodiments, gel permeation chromatography (GPC) analysis of compound 1800 using polystyrene (PS) standards shows number average molecular weight M _n = 4.36 kg mol ^-1 (toluene) and 11.2 kg mol ^-1 (THF). ) And the weight average molecular weights M _w = 6.1 kg mol ^-1 (toluene) and 20.8 kg mol ^-1 (THF), indicating that the polydispersity index (PDI) is 1.87 (toluene) and 1.39 (THF). ..

In some embodiments, conversion from 1800 to polymer 1802 was ^{confirmed by 1} H and ¹³ C NMR spectroscopy (eg, FIGS. 35 and 36). In polymer 1800, the ^{peak disappeared at 8.32 ppm in 1} H NMR (due to Hx, see Figure 35). ^{13 In} C NMR, the alkyne signal disappeared (88.1 and 94.1 ppm, see Figure 36). In some embodiments, the disappearance of the alkyne signal in the IR spectra of the polymers 1800 and GNR1802, as well as the integration, can be interpreted to support that cyclization has occurred, with some embodiments exceeding 95%. It was confirmed that cyclization of the above occurred (see, for example, FIGS. 37 and 38).

In some embodiments, the Raman spectrum of the nanostructure compound 1802, D- band (1300~1500cm ^-1), G- band (1500~1600cm ^-1), 2D- band (2600~2800cm ^-1), and The D + G-band (2900-3000 cm ^-1 ) and other characteristic points that may be expected with graphene nanoribbons are shown. In a typical embodiment, the 1802 Raman spectrum also contains GNR feature points (11, 14, 26), which are typical D-bands (1345 cm ^-1 ) and G-bands (1595 cm ^-1 ). Shown (FIGS. 26 and 27). Well-resolved double resonance signals were also ^{observed at 2690, 2940, and 3190 cm -1} , which can be assigned to the 2D, D + G, and 2G bands, respectively. ^{In addition, there is a separate peak ~ 235 cm -1} that may be due to radial breathing-like mode (RBLM), showing high uniformity of polymer 1802 width.

In yet another embodiment, the isotope pattern corresponding to the expected distribution can be observed, so that MALDI-TOF mass spectrometry is used to ensure that some embodiments of the polymer structure have a nanoribbon structure. It is possible to confirm. In yet another embodiment, the structure of polymer 1802 can also be characterized by UV-vis spectroscopy. For example, in some embodiments, the UV-vis spectrum of 1800 in _{CH 2} Cl _{2 solution showed relatively high energy and rapid absorption (λ max} = 309 nm). After aromatic cyclization reaction, 1802 but there is a low energy broad absorption which were observed to absorb to the near IR from UV region beyond the visible region (Fig. _{28) λ max ~700nm (1.77eV)} , it is faded, The absorption edge is ~ 1200 cm ^-1 (1.03 eV).

In yet another embodiment, transmission electron microscopy (TEM) can be performed on the compounds disclosed herein (as shown by FIGS. 39A-39G). In some embodiments, the polymer sample is placed on a lace-like carbon grid. At low magnification, the polymer compound can be in the form of large thin films that can result from polymer aggregation during solvent evaporation (see, eg, FIG. 39F). In some representative embodiments, HRTEM images showed regions with multiple layers of polymeric compounds (FIGS. 39B, 39C, 39E, and 39G). The region with the curved layer showed that the polymer compound was flexible (Fig. 39B). In an exemplary embodiment, a monolayer film formed by 1802 was detected, which clearly showed a polymer with a single band (or ribbon) of 1802 (FIGS. 39E and 39G). The width of 1802 is about 0.5 nm, which is in agreement with the theoretical value. The distance between the two ribbons of 1802 (about 0.2 nm) is narrower than the width of 1802 when including the side chains, indicating that partial stacking of nanostructures is possible. The bundle of polymer compounds shown in FIG. 39G is in the range of about 8-25 nm, which is consistent with the GPC calculation results. The restricted field electron analysis (SAED) pattern obtained from polymer 1802 showed the crystallinity of the sample and showed a hexagonal pattern peculiar to graphene (Fig. 39D).

In yet another embodiment, a scanning tunneling microscope (STM) of the polymeric compounds disclosed herein at the solid-liquid interface of highly oriented pyrolytic graphite (HOPG) / 1,2,4-trichlorobenzene (TCB). I was able to get an image. After placing the nanostructures from the TCB dispersion (eg 1802) on the HOPG substrate, the nanostructures showed parallel aggregation that could also be confirmed by TEM (FIGS. 40, 39E, and 39G). The nanostructures also showed an extension along one dimension, which was observed to be over 100 nm in length (Fig. 40). Ribbon length (7-20 nm, FIG. 40) is consistent with the results of GPC and TEM characterization methods. The pattern seen in the STM image shows alternating height regions, suggesting that the aryl substituents on the ribbon are staggered up and down, which is the two intermolecular H ... H repulsive force: can be explained by two phenyl groups away from the skeleton and by the phenyl group and the bay region hydrogen, which results in a significant tilt towards the surface of the latter (eg, FIG. 40). The semi-empirical method (PM3) was used on the 1802 short model to better understand this alternating pattern. The results confirm that the aryl groups are staggered up and down (eg, FIG. 40). The periodicity (~ 1.16 nm) observed with this aryl substituent is approximately the same as the longitudinal length (~ 0.9 nm) of one repeating unit, with a nanostructure width of 1802 (~ 1 nm, 2 separated from the skeleton). Including one phenyl, FIG. 40) was also close to the calculated value (about 1.1 nm).

IV. Examples Experimental Section Overview-Chemicals and solvents were purchased from Oakwood Products Inc. and Sigma-Aldrich and used immediately without further purification unless otherwise stated. Anhydrous tetrahydrofuran (THF) and dichloroethane (DCM) were obtained by passing the solvent (HPLC grade) through an activated alumina column of the JC Meyer solvent drying system. All reactions dealing with air-sensitive or moisture-sensitive compounds were performed in a nitrogen-dried reaction vessel.

¹ H and ¹³ C NMR spectra were recorded on a Varian 400 MHz or Varian 500 MHz NMR Systems Spectrometer. The spectrum was recorded in deuterated chloroform (CDCl _3). Tetramethylsilane (TMS, set to 0 ppm) was used as an internal standard for chemical shift. For reference, the solvent peaks (7.26 ppm at ^{1 H, 77.16 ppm at 13} C). Chemical shifts are reported in low to high frequency parts per million (ppm) and are relative to residual solvent resonance. The coupling constant (J) is reported in Hz. The multiplicity of the 1H signal is s = singlet (singlet), d = doublet (doublet), t = triplet (triplet), dd = double doublet (double doublet), m = multiplet (multiplet), br = broad (broad). ).

Mass spectra were recorded using an Agilent 6230 TOF MS. The equipment was operated with an atmospheric pressure photoionization (APPI) source for time-of-flight (TOF) equipment in positive mode. Toluene was added to the sample to promote ionization.

UV visible and fluorescence spectra were obtained at ambient temperature; λ (unit: nm) (ε (unit: L · mol ^-1 · cm ^-1 )).

High resolution ESI mass spectrometry was recorded using an Agilent 6230 TOF MS. TFA was added to the sample to promote ionization.

Solution UV-vis absorption spectra were recorded with a Perkin-Elmer Lambda 900 spectrophotometer at room temperature.

With respect to Scheme 8, various techniques can be used to determine the products and intermediates associated with the production of the peropylene compounds disclosed herein. In some embodiments, the ¹ H NMR spectrum, UV-vis spectrum, and fluorescence spectrum showed significant differences. ¹ H NMR spectrum comparison shows that the anti-shielding effect of the alkyne causes the flattened picene to form a bis-cyclyzed product, resulting in a substantial reduction in the signal of the proton in the recessed position to 10.39 ppm. It was revealed to show a field shift (12b, FIG. 48A). Moreover, the wide peaks appearing in the aromatic region should be due to the two phenyl rings in the picene. This is because the Ar groups are too close to each other and their free rotation is limited. It was confirmed that the wide peaks did not correlate with the bonds of the other two phenyl groups of the alkyne in the ROESY and NOESY spectra, and that neither intermediates 712 nor 714 were formed (Fig. 2, respectively). And 3). The anti-shielding effect of alkynes becomes stronger as the whole system is more flattened in the tri-cyclized product, which further downfields the signal of protons in recessed positions to 10.71 ppm. It was shifted (12c, FIG. 48A). ¹ H NMR of methoxy groups represents much more directly, with compounds 702a-d and 704a-d showing one singlet because they are centrally symmetric, while line-symmetric compounds 702a-d show two singlets. In the asymmetric compounds 708a-d, four different singlets were shown (FIG. 48B).

As the cyclization reaction was gradually completed, the entire compound backbone was more conjugated, which was clearly reflected in the UV-vis absorption and fluorescence emission spectra (FIGS. 4 and 5). Additional images of representative compounds are provided in FIGS. 8 and 9, including absorption and fluorescence spectra. From the UV-vis absorption spectrum, it was observed that the maximum absorption peak moved to a longer wavelength as the cyclization was completed (293, 345, 510 nm). The maximum emission peak also moved to longer wavelengths (389, 432, 530 nm).

Synthesis and characterization

Compound 104a: 102a (0.681 g, 5.15 mmol), bis (triphenylphosphine) palladium II dichloride (0.324 g, 0.462 mmol), in a 100 bistriflate solution (1.0 g, 2.22 mmol) dissolved in anhydrous DMF (75 mL), Tetraethylammonium iodide (1.15 g, 4.47 mmol), triethylamine (4.02 mL, 54.7 mmol), and copper (I) iodide (0.180 g, 0.945 mmol) were added in this order. The flask was heated to 85 ° C. and stirred for about 18 hours until confirmed by TLC to be complete. The reaction was quenched with saturated aqueous ammonium chloride solution at room temperature and absorbed with 100 mL of diethyl ether to separate the layers. The organic phase was washed with saturated aqueous ammonium chloride solution (3 x 50 mL) and brine (3 x 50 mL), dried over DDL ₄ and the mixture filtered. The solvent was removed in vacuo and the crude product was purified by column chromatography (silica gel, 1: 1 CH ₂ Cl ₂ / benzene) to produce 104a (446 mg, 48%) as a white crystalline solid: ¹ H NMR. (400 MHz, CDCl ₃ ): δ 7.55-7.51 (m, 2H), 7.46 (d, 2H), 7.41-7.30 (m, 3H), 7.18 (t, 1H), 7.07-7.02 (m, 4H), 6.69-6.65 (m, 4H), 3.65 (s, 6H); ¹³ C NMR (500 MHz, CDCl ₃ ): δ 143.1, 139.6, 139.1, 136.6, 130.6, 129.6, 127.9, 127.7, 127.0, 112.6, 0.2.

Compound 104b: 102b (1.79 g, 5.63 mmol), bis (triphenylphosphine) palladium II dichloride (0.096 g, 0.137 mmol), triethylamine (1.86) in 100 solutions (0.539 g, 2.67 mmol) dissolved in THF (50 mL). mL, 13.3 mmol), and copper (I) iodide (0.105 g, 0.551 mmol) were added in this order. The flask was left at room temperature and stirred for about 18 hours until confirmed by TLC to be complete. The reaction was quenched with saturated aqueous ammonium chloride solution at room temperature and absorbed with 100 mL of diethyl ether to separate the layers. The organic phase was washed with saturated aqueous ammonium chloride solution (3 x 50 mL) and brine (3 x 50 mL), dried over DDL ₄ and the mixture filtered. The solvent was removed in vacuum and the crude product was purified by column chromatography (silica gel, 1: 5 CH ₂ Cl ₂ / hexane) to produce 104b (552 mg, 34%) as yellow oil: ¹ H NMR (500 MHz). , CDCl ₃ ): δ 7.64-7.60 (m, 2H), 7.56 (d, 2H), 7.51-7.40 (m, 3H), 7.29 (t, 1H), 7.15-7.10 (m, 4H), 6.81-6.76 (m, 4H), 3.85-3.78 (m, 4H), 1.76-1.67 (m, 2H), 1.55-1.25 (m, 18H), 0.96-0.87 (m, 13H); ¹³ C NMR (500 MHz, CDCl ₃ ): δ 159.4, 145.8, 139.3, 132.7, 131.4, 130.4, 127.4, 127.3, 127.0, 123.5, 115.0, 114.4, 93.1, 87.6, 70.5, 53.4, 39.3, 30.5, 29.0, 23.8, 23.0, 14.1, 11.1.

Compound 104e: 102e (1.76 g, 6.22 mmol), bis (triphenylphosphine) palladium II dichloride (0.088 g, 0.125 mmol), triethylamine (1.73) in 100 solutions (0.503 g, 2.49 mmol) dissolved in THF (50 mL). mL, 12.4 mmol), and copper (I) iodide (0.101 g, 0.530 mmol) were added in this order. The flask was left at room temperature and stirred for about 18 hours until confirmed by TLC to be complete. The reaction was quenched with saturated aqueous ammonium chloride solution at room temperature and absorbed with 100 mL of diethyl ether to separate the layers. The organic phase was washed with saturated aqueous ammonium chloride solution (3 x 50 mL) and brine (3 x 50 mL), dried over DDL ₄ and the mixture filtered. The solvent was removed in vacuum and the crude product was purified by recrystallization (oversaturation in hot toluene; powdered with cold hexane) to give 104e (292 mg, 23%) as a beige powder solid: ¹ 1 H NMR (500 MHz, CDCl ₃ ): δ 7.62-7.55 (m, 4H), 7.51-7.41 (m, 3H), 7.40-7.36 (m, 4H), 7.33 (t, 1H), 7.05-7.01 (m) , 4H); ¹³ C NMR (500 MHz, CDCl ₃ ): δ 146.5, 138.9, 132.7, 132.2, 131.5, 130.2, 127.7, 127.4, 127.2, 123.0, 122.5, 122.0, 92.0, 89.8.

Compound 104f: 102f (0.518 g, 2.08 mmol), bis (triphenylphosphine) palladium II dichloride (0.040 g, 0.057 mmol), triethylamine (0.690) in 100 solutions (0.205 g, 1.01 mmol) dissolved in THF (50 mL). mL, 4.95 mmol), and copper (I) iodide (0.046 g, 0.242 mmol) were added in this order. The flask was left at room temperature and stirred for about 18 hours until confirmed by TLC to be complete. The reaction was quenched with saturated aqueous ammonium chloride solution at room temperature and absorbed with 100 mL of diethyl ether to separate the layers. The organic phase was washed with saturated aqueous ammonium chloride solution (3 x 50 mL) and brine (3 x 50 mL), dried over DDL ₄ and the mixture filtered. The solvent was removed in vacuum and the crude product was purified by recrystallization (oversaturation in hot toluene; powdered with cold hexane) to produce 104f (270 mg, 60%) as an orange powder solid: ¹ H NMR. (500 MHz, CDCl ₃ ): δ 8.15-8.10 (m, 4H), 7.69 (d, 2H), 7.60-7.56 (m, 2H), 7.55-7.48 (m, 3H), 7.41 (t, 1H) 7.31 -7.27 (m, 4H); ¹³ C NMR (500 MHz, CDCl ₃ ): δ 147.5, 147.0, 138.6, 133.1, 132.0, 130.1, 129.8, 128.1, 127.6, 127.5, 123.5, 122.4, 93.6, 91.3.

Compound 104 g: 102 g (0.910 g, 6.19 mmol), bis (triphenylphosphine) palladium II dichloride (0.089 g, 0.127 mmol), triethylamine (1.72) in 100 solutions (0.500 g, 2.47 mmol) dissolved in THF (150 mL). mL, 12.3 mmol), and copper (I) iodide (0.100 g, 0.525 mmol) were added in this order. The flask was left at room temperature and stirred for about 18 hours until confirmed by TLC to be complete. The reaction was quenched with saturated aqueous ammonium chloride solution at room temperature and absorbed with 100 mL of diethyl ether to separate the layers. The organic phase was washed with saturated aqueous ammonium chloride solution (3 x 50 mL) and brine (3 x 50 mL), dried over DDL ₄ and the mixture filtered. The solvent was removed in vacuum and the crude product was purified by column chromatography (silica gel, 1: 6CH ₂ Cl ₂ / hexane) to produce 104 g (480 mg, 40%) as a beige powder solid: ¹ H NMR (1 H NMR). 500 MHz, CDCl ₃ ): δ 7.65 (d, 2H), 7.61-7.57 (m, 2H), 7.54-7.44 (m, 7H), 7.37 (t, 1H), 7.29-7.26 (m, 4H); ¹³ C NMR (500 MHz, CDCl ₃ ): δ 147.1, 138.8, 138.0, 132.6, 131.5, 130.2, 130.0, 129.7, 127.9, 127.5, 127.3, 126.8, 125.2, 125.1, 125.0, 122.7, 91.7, 90.9.

Compound 108a: 50 μL of undiluted solution (1 mL of trifluic acid dissolved in _{49 mL of CH 2} Cl ₂ in a sealed Schlenk tube) was added to a flask containing _{CH 2} Cl _{2 (10 mL). CH 2} Cl ₂ (10 mL) was added to another flask containing 104a (0.065 g, 0.106 mmol). The resulting solution was taken into a syringe and slowly added dropwise to the first flask at room temperature for at least 1 hour. The flask was left at room temperature and stirred for about 24 hours until confirmed by TLC to be complete. The reaction was quenched with saturated aqueous sodium hydroxide solution at room temperature to separate the layers. The organic phase was washed with saturated aqueous sodium hydroxide solution (2 x 20 mL) and H ₂ O (2 x 20 mL), dried over DDL ₄ and the mixture filtered. The solvent was removed in vacuum and the crude product was purified by column chromatography (silica gel, 1: 5 CH ₂ Cl ₂ / hexane) to produce 108a (52 mg, 80%) as yellow oil: ¹ H NMR (1 H NMR). 500 MHz, CDCl ₃ ): δ 8.28 (d, 2H), 8.19 (d, 2H), 8.06-8.02 (m, 3H), 7.91 (t, 1H), 7.63-7.59 (m, 4H) 7.10-7.15, 4.03-3.96 (m, 4H), 1.84 (sp, 2H), 1.67-1.36 (m, 19H), 1.05-0.95 (m, 13H); ¹³ C NMR (500 MHz, CDCl ₃ ): δ159.0, 139.4 , 133.0, 131.1, 131.0, 130.8, 127.6, 126.3, 125.4, 125.4, 124.7, 124.1, 123.6, 114.4, 39.5, 30.6, 29.1, 24.0, 23.1, 14.1, 11.2.

Compound 108b: 50 μL of stock solution (1 mL of trifluic acid dissolved in _{49 mL of CH 2} Cl ₂ in a sealed Schlenk tube) was added to a flask containing _{CH 2} Cl _{2 (10 mL). CH 2} Cl ₂ (10 mL) was added to another flask containing 104b (0.065 g, 0.106 mmol). The resulting solution was taken into a syringe and slowly added dropwise to the first flask at room temperature for at least 1 hour. The flask was left at room temperature and stirred for about 24 hours until confirmed by TLC to be complete. The reaction was quenched with saturated aqueous sodium hydroxide solution at room temperature to separate the layers. The organic phase was washed with saturated aqueous sodium hydroxide solution (2 x 20 mL) and H ₂ O (2 x 20 mL), dried over DDL ₄ and the mixture filtered. The solvent was removed in vacuum and the crude product was purified by column chromatography (silica gel, 1: 5 CH ₂ Cl ₂ / hexane) to produce 108b (52 mg, 80%) as yellow oil: ¹ H NMR (1 H NMR). 500 MHz, CDCl ₃ ): δ 8.28 (d, 2H), 8.19 (d, 2H), 8.06-8.02 (m, 3H), 7.91 (t, 1H), 7.63-7.59 (m, 4H) 7.10-7.15, 4.03-3.96 (m, 4H), 1.84 (sp, 2H), 1.67-1.36 (m, 19H), 1.05-0.95 (m, 13H); ¹³ C NMR (500 MHz, CDCl ₃ ): δ 159.0, 139.4, 133.0, 131.1, 131.0, 130.8, 127.6, 126.3, 125.4, 125.4, 124.7, 124.1, 123.6, 114.4, 39.5, 30.6, 29.1, 24.0, 23.1, 14.1, 11.2.

Synthesis of compound 306
2-Bromo-5- (tert-butyl) -1,3-diiodobenzene 304 (4.65 g, 10 mmol, 1.0 eq) dissolved in Et _{3 N (40 mL) and THF (80 mL) and terminal alkyne (2.5 eq)} Pd (PPh ₃ ) ₂ Cl ₂ (70 mg, 0.1 mmol) and CuI (38 mg, 0.2 mmol) were added to the solution of. The resulting mixture was _{stirred in an N 2} atmosphere at room temperature for 14 hours. The ammonium salt was then removed by filtration. The solvent was removed under reduced pressure and the residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give the corresponding product 306.

306a (4.3 g, 91%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.53 (d, J = 8.7 Hz, 2H), 7.48 (s, 1H), 6.88 (d, J = 8.7 Hz, 2H) , 3.98 (t, J = 6.5 Hz, 2H), 1.83 --1.75 (m, 2H), 1.45 (m, 2H), 1.31 (m, 17H), 0.89 (t, J = 6.8 Hz, 3H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.69, 150.14, 133.35, 133.26, 129.80, 126.16, 125.06, 114.87, 114.71, 93.71, 87.53, 68.25, 34.70, 32.05, 31.18, 29.73, 29.71, 29.55, 29.48, 29.34, 26. , 22.84, 14.28. HRMS (ESI, positive) m / z calcd for C ₂₈ H ₂₅ BrO ₂ [M] ⁺ 472.1038, found 472.1043 (see Figures 10A and 10B for NMR spectra).

306b (4.3 g, 86%). ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.55 (d, J = 8.9 Hz, 4H), 7.49 (s, 2H), 6.90 (d, J = 8.9 Hz, 4H) , 3.84 (s, 6H), 1.33 (s, 9H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 160.09, 150.18, 133.48, 133.39, 133.31, 133.24, 129.95, 129.85, 129.75, 126.14, 125.10, 115.18, 114.48, 114.39, 114.20, 114.02, 113.91, 113.73, 93.60, 87.62, 55.58, 55.39, 34.71, 31.25, 31.18, 31.10. HRMS (ESI, positive) m / z calcd for C ₂₈ H ₂₅ BrO ₂ [M] ⁺ 472.1038 , Found 472.1043 (see Figures 11A and 11B for NMR spectra).

306c (5.76 g, 87%). ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.55 (d, J = 8.9 Hz, 2H), 7.51 (s, 1H), 6.91 (d, J = 8.9 Hz, 2H) , 3.88 (dd, J = 5.8, 0.9 Hz, 2H), 1.78 --1.71 (m, 1H), 1.54 --1.41 (m, 4H), 1.37 --1.32 (m, 9H), 0.97 --0.90 (m, 6H) . ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.93, 150.11, 133.30, 129.74, 126.20, 125.08, 114.81, 114.73, 93.78, 87.53, 77.41, 77.16, 76.91, 70.71, 39.47, 34.67, 31.15, 30.64, 29.22, 23.98, 23.18, 14.23, 11.26. HRMS (ESI, positive) m / z calcd for C ₄₂ H ₅₃ BrO ₂ [M] ⁺ 668.3229, found 668.3219 (see Figures 12A and 12B for NMR spectra).

306d (4.24 g, 69%). R _f = 0.25 (hexane / DCM 10: 1). FTIR (neat) 2953, 2940, 2208, 1603, 1562, 1508, 1472, 1936, 1284, 1245, 1172, 1024, ^{829 cm -1. 1 H NMR (} 400 MHz, cdcl 3) δ 7.53 (d, J = 8.7 Hz, 4H), 7.49 (s, 2H), 6.89 (d, J = 8.8 Hz, 4H), 3.98 (t , J = 6.6 Hz, 4H), 1.82 --1.76 (m, 4H), 1.50 --1.33 (m, 21H), 0.92 (t, J = 6.9 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 70, 150.14, 133.35, 129.79, 126.18, 125.07, 114.89, 114.72, 93.73, 87.54, 68.26, 34.70, 31.73, 31.17, 29.31, 25.85, 22.75, 14.19.

Synthesis of compound 700:
A solution of n-butyllithium hexane (5 mL, 2.5 M, 1.25 eq) was added to a solution of aryl 306 bromide (10 mmol, 1.0 eq) dissolved in THF (50 mL) at −78 ° C. After stirring at −78 ° C. for 1 hour, isopropoxyboronic acid pinacol ester (2.79 g, 15 mmol, 1.5 eq) was added, and the reaction was removed from the cooling tank and warmed. The reaction was cooled by adding _{H 2} O at room temperature and then extracted with DCM. The extract was washed with water, dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. The residue was purified by flash column chromatography (SiO ₂ , hexane / DCM) to give the corresponding product 700.

700a (3.49 g, 67%). ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.48 (s, 2H), 7.45 (d, J = 8.7 Hz, 4H), 6.85 (d, J = 8.7 Hz, 4H) , 3.96 (t, J = 6.6 Hz, 4H), 1.82 --1.75 (m, 4H), 1.38 --1.25 (m, 49H), 0.89 (t, J = 6.6 Hz, 6H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.26, 152.27, 133.09, 128.75, 126.87, 115.54, 114.58, 89.98, 88.84, 84.26, 77.41, 77.16, 76.91, 68.20, 34.78, 32.05, 31.14, 29.72, 29.70, 29.54, 29.47, 29.37, 26. 25.15, 22.83, 14.26. HRMS (ESI, positive) m / z calcd for C ₃₄ H ₃₇ BO ₄ Na [M + Na] ⁺ 543.2683, found 543.2690 (See Figures 13A and 13B for NMR spectra).

700b (3.49 g, 59%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.52 (s, 2H), 7.49 (d, J = 7.6 Hz, 4H), 6.88 (d, J = 7.6 Hz, 4H) , 3.80 (s, 6H), 1.36 (d, J = 27.2 Hz, 21H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.64, 152.29, 133.10, 129.65, 128.77, 126.83, 115.79, 114.05, 89.87, 88.91 , 84.26, 55.39, 34.77, 31.44, 31.12, 25.14. HRMS (ESI, positive) m / z calcd for C ₃₄ H ₃₇ BO ₄ Na [M + Na] ⁺ 543.2683, found 543.2690 (FIGS. 14A and 14B for NMR spectra. See).

700c (4.23 g, 61%). ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.53 (s, 1H), 7.50 (d, J = 8.9 Hz, 2H), 6.90 (d, J = 8.9 Hz, 2H) , 3.87 (d, J = 5.9 Hz, 2H), 1.78 --1.71 (m, 1H), 1.56 --1.44 (m, 4H), 1.40 (s, 6H), 1.38 --1.31 (m, 9H), 0.97 --0.91 (m, 6H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.40, 152.04, 132.91, 128.51, 126.88, 115.38, 114.49, 89.98, 88.74, 84.05, 70.48, 39.39, 34.57, 31.62, 30.99, 30.55, 29.12 , 25.01, 23.89, 23.06, 22.68, 14.10, 11.15. HRMS (ESI, positive) m / z calcd for C ₄₈ H ₆₆ BO ₄ [M + H] ⁺ 717.5054, found 717.5053 (See Figures 15A and 15B for NMR spectra. reference).

700d (4.19 g, 63%). R _f = 0.20 (hexane / DCM 4: 1). FTIR (neat) 2954, 2931, 2869, 2205, 1605, 1587, 1508, 1467, 1331, 1315, 1245, 1133, ^{854, 829 cm -1. 1 H} NMR (400 MHz, cdcl 3) δ 7.48 (s, 2H), 7.45 (d, J = 8.8 Hz, 4H), 6.86 (d, J = 8.8 Hz, 4H), 3.97 (t, J = 6.6 Hz, 4H), 1.81 --1.75 (m, 4H), 1.46 --1.30 (m, 37H), 0.91 (t, J = 6.9 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃₎ ) δ 159. 25, 152.25, 133.08, 128.73, 126.86, 115.52, 114.56, 89.97, 88.83, 84.25, 68.18, 34.76, 31.72, 31.13, 29.32, 25.85, 25.14, 22.74, 14.17.

Synthesis of trimer 702:
Anhydrous 1,4-diiodobenzene (0.33 g, 1 mmol, 0.5 eq), 2,6-diynylphenylborate 700 (2 mmol, 1.0 eq), and Ag ₂ CO ₃ (1.1 g, 4 mmol, 2.0 eq) Dissolved in THF (60 mL). Pd (PPh ₃ ) ₄ (231 mg, 0.2 mmol, 0.1 eq) was added and then the mixture was degassed by bubbling nitrogen for 30 minutes. The resulting mixture was _{stirred under an N 2} atmosphere at 80 ° C. for 24 hours. After the reaction was complete, the mixture was diluted with DCM _{, washed with H 2} O and dried over Na ₂ SO ₄ . The solvent was removed under reduced pressure and the residue was purified by column chromatography (SiO2, hexane / DCM) to give the desired facing sandwich-like trimer 702.

702a (0.45 g, 57%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.76 (s, 4H), 7.70 (s, 4H), 7.09 (d, J = 8.7 Hz, 8H), 6.56 (d, J = 8.8 Hz, 8H), 3.80 (t, J = 6.6 Hz, 8H), 1.74 --1.69 (m, 8H), 1.50 --1.31 (m, 74H), 0.94 (t, J = 6.9 Hz, 12H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 158.95, 150.05, 143.64, 138.80, 132.92, 129.59, 128.53, 123.56, 115.04, 114.30, 93.05, 88.22, 67.94, 34.70, 32.05, 31.36, 29.73, 29.71, 29.53, 29.48 , 29.28, 26.15, 22.83, 14.26. HRMS (ESI, positive) m / z calcd for C ₆₂ H ₅₄ O ₄ [M] ⁺ 862.4022, found 862.4012 (see Figures 16A and 16B for NMR spectra).

702b (0.45 g, 65%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.71 (s, 2H), 7.65 (s, 2H), 7.04 (d, J = 8.8 Hz, 4H), 6.53 (d, J = 8.8 Hz, 4H), 3.64 (s, 6H), 1.45 (s, 9H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.35, 150.15, 143.68, 138.82, 132.95, 129.59, 128.62, 123.50, 115.31 , 113.77, 92.90, 88.30, 77.41, 77.16, 76.91, 55.24, 34.76, 31.38. HRMS (ESI, positive) m / z calcd for C ₆₂ H ₅₄ O ₄ [M] ⁺ 862.4022, found 862.4012 17A and 17B).

702c (0.76 g, 63%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.72 (s, 1H), 7.66 (s, 1H), 7.05 (d, J = 8.8 Hz, 2H), 6.54 (d, J = 8.8 Hz, 2H), 3.69 --3.64 (m, 2H), 1.66 --1.61 (m, 1H), 1.46 (s, 5H), 1.43 --1.28 (m, 10H), 0.93 --0.88 (m, 6H) . ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.22, 150.07, 143.70, 138.81, 132.92, 129.61, 128.51, 123.58, 114.98, 114.36, 93.09, 88.20, 77.41, 77.16, 76.91, 70.50, 39.39, 34.75, 31.75, 31.39, 30.63, 29.20, 23.95, 23.19, 22.81, 14.22, 11.21. HRMS (ESI, positive) m / z calcd for C ₉₀ H ₁₁₀ O ₄ [M] ⁺ 1254.8404, found 1254.8371 (FIGS. 18A and 18B for NMR spectra) See).

702d (0.76 g, 66%) ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 7.78 (s, 4H), 7.71 (s, 4H), 7.10 (d, J = 8.7 Hz, 8H), 6.58 (d, J = 8.8 Hz, 8H), 3.80 (t, J = 6.5 Hz, 8H), 1.76 --1.68 (m, 8H), 1.51 --1.34 (m, 42H), 0.95 (t, J = 6.8 Hz, 12H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 157. 99, 149.51, 139.93, 136.56, 131.59, 128.12, 126.09, 124.10, 122.79, 120.43, 68.34, 35.34, 32.06, 31.86, 29.53, 25.95, 22.83, 14.26.

Synthesis of dicyclized trimer 704b:
In a heat-dried flask under a nitrogen atmosphere, 702b (100 mg, 0.11 mmol) was dissolved in anhydrous DCM (50 mL) and cooled to 0 ° C. Methanesulfonic acid (3 drops) was added to the solution by syringe. The reaction mixture was stirred for 1 hour and then _{cooled with saturated acrylamide 3} aqueous solution (1.0 mL). The mixture was washed with H ₂ O (2 x 20 mL) and dried over Na ₂ SO ₄ . The solvent was then removed under reduced pressure and the residue was purified by column chromatography (SiO ₂ , hexane / DCM, 80/20, v / v) as a yellow solid with dicyclized trimer 704b (97 mg, 97%). ) Was obtained. ¹ H NMR (500 MHz, CDCl ₃ ) δ 10.40 (s, 1H), 8.07 (d, J = 2.2 Hz, 1H), 7.85 (d, J = 2.1 Hz, 1H), 7.68 --7.64 (m, 2H) , 7.39 (s, 1H), 6.87 --6.83 (m, 2H), 6.43 --6.78 (br, 4H), 3.82 (d, J = 1.9 Hz, 6H), 1.53 (s, 9H). ¹³ C NMR (126) MHz, CDCl ₃ ) δ 159.81, 158.39, 148.60, 140.11, 136.33, 133.38, 132.95, 132.54, 131.38, 128.64, 128.54, 126.49, 125.30, 123.47, 119.40, 116.06, 114.34, 94.39, 91.68, 77.42, 77.16, 76. 55.49, 55.38, 34.76, 31.73, 31.42, 22.80, 14.27. HRMS (ESI, positive) m / z calcd for C ₆₂ H ₅₄ O ₄ [M] ⁺ 862.4022, found 862.4016 (See Figures 20A and 20B for NMR spectra. ). In some embodiments, the structures of 702b, 704b, and 706b were optimized by Merck Molecular Force Field 94 (MMFF94) calculations as shown in FIG. 7 (gray, carbon; white, hydrogen; red, oxygen). ..

The 704a and 704c could also be prepared according to the same procedure.

704a: ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 10.36 (s, 2H), 8.03 (d, J = 1.9 Hz, 2H), 7.81 (d, J = 1.8 Hz, 2H), 7.63 (d, J = 8.6 Hz, 4H), 7.36 (s, 2H), 6.83 (d, J = 8.7 Hz, 4H), 6.48 --6.57 (br, 8H), 4.03 --3.87 (m, 8H), 1.81 (d, J = 6.0) Hz, 8H), 1.55 --1.21 (m, 74H), 0.90 (m, 12H). ¹³ C NMR (126 MHz, cdcl ₃ ) δ 159. 29, 157.77, 148.38, 140.06, 136.03, 133.25, 132.79, 132.31, 131.22, 128.46, 128.42, 126.33, 125.09, 123.32, 119.30, 115.65, 114.72, 94.35, 91.46, 68.15, 68.09, 34.61, 31.93, 31.29, 29.64, 29.61, 29.50, 29.48, 29.38, 29.36, 29.29, 26.10 22.71, 14.14. HRMS (ESI, positive) m / z calcd for C ₆₂ H ₅₄ O ₄ [M] ⁺ 862.4022, found 862.4016 (See Figures 19A and 19B for NMR spectra).

704c: ^{1 1} H NMR (500 MHz, cdcl ₃ ) δ 10.39 (s, 2H), 8.08 (d, J = 2.1 Hz, 2H), 7.87 (d, J = 2.1 Hz, 2H), 7.68 (d, J = 8.8 Hz, 4H), 7.41 (s, 2H), 6.90 (d, J = 8.8 Hz, 4H), 6.25-6.71 (br, 8H), 3.92 --3.86 (m, 8H), 1.80 (m, 5H), 1.56 (s, 21H), 1.52 --1.36 (m, 31H), 1.04 ^{--0.96 (m, 24H). 13} C NMR (126 MHz, cdcl ₃ ) δ 159. 71, 158.21, 158.20, 148.52, 140.27, 136.13, 133.39, 132.92, 132. 39, 131.37, 128.65, 128.60, 126.53, 125.19, 123.51, 119.47, 115.73, 114.90, 94.50, 91.58, 77.41, 77.16, 76.91, 70.93, 70.91, 70.79, 70.77, 39.56, 39.51, 34.76, 31.50, 31.44, 30.73, 30.67, 30.65, 29.30, 29.26, 29.24, 24.05, 24.00, 23.99, 23.28, 23.25, 23.24, 23.22, 14.30, 14.25, 11.30, 11.29, 11.27, 11.26. HRMS (ESI, positive) m / z calcd for C ₆₂ H ₅₄ O ₄ [M] ⁺ 862.4022, found 862.4016 (See Figures 21A and 21B for NMR spectra).

704d (97 mg, 97%) ¹ H NMR (400 MHz, cdcl ₃ ) δ 10.35 (s, 2H), 8.02 (s, 2H), 7.80 (s, 2H), 7.61 (d, J = 7.4 Hz, 4H ), 7.35 (s, 2H), 6.81 (d, J = 8.3 Hz, 4H), 6.52 (br, 8H), 3.97 --3.86 (m, 8H), 1.83 --1.74 (m, 8H), 1.50 --1.33 ( m, 42H), 0.92 (d, J = 2.4 Hz, 12H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 43, 157.90, 148.53, 140.20, 136.15, 133.39, 132.92, 132.45, 131.35, 128.59, 128.55, 126.46, 125.22, 123.46, 119.44, 115.77, 114.85, 94.50, 91.60, 68.26, 68.19, 53.53, 34.74, 31.82, 31.76, 31.41, 29.46, 29.36, 25.90, 25.88, 22.79, 22.76, 14.22, 14.19.

Synthesis of tricyclic trimer 706b
0.1 mL of trifluic acid at −40 ° C. was added to a 704b solution (50 mg, 0.058 mmol) dissolved in 20 mL of anhydrous CH ₂ Cl _2. After 1 hour, TLC showed that the reaction was complete. The solution was _{cooled with saturated LVDS 3} solution (2.0 mL) and then _{washed with H 2} O (2 x 10 mL). The solvent was dried (Na ₂ SO ₄ ) and removed under reduced pressure. The residue was purified by column chromatography (1: SiO ₂ , hexane / DCM, 75/25, v / v; second: neutral Al ₂ O ₃ , toluene) and tricyclized trimer 706b (21 mg). , 43%) was obtained as an orange solid. ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 8.23 (s, 2H), 7.79 (s, 2H), 6.51 --6.91 (br, 8H), 3.85 (s, 6H), 1.62 (s, 9H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 158.48, 149.59, 139.83, 136.74, 131.57, 128.23, 126.11, 124.06, 122.89, 120.46, 55.60, 35.36, 32.06. HRMS (ESI, positive) m / z calcd for C ₆₂ H ₅₄ O ₄ [M] ⁺ 862.4022, found 862.3993 (see Figures 23A and 23B for NMR spectra).

One-step synthesis of tricyclic trimer 706:
In a heat-dried flask under a nitrogen atmosphere, 702 (0.08 mmol) was dissolved in anhydrous DCM (50 mL) and cooled to 0 ° C. Methanesulfonic acid (5 drops) was added to the solution by syringe. After 1 hour, the reaction was cooled to −40 ° C., then 0.1 mL of trifluic acid was added and the reaction was continued for an additional 1 hour. The solution was _{cooled with saturated LVDS 3} solution (2.0 mL) and then _{washed with H 2} O (2 x 20 mL). The solvent was dried (Na ₂ SO ₄ ) and removed under reduced pressure. The residue was purified by column chromatography (1: SiO ₂ , hexane / DCM; second: neutral Al ₂ O ₃ , hexane / toluene) to obtain tricyclized trimer 706.

706a (41 mg, 38%). ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 8.22 (s, 4H), 7.79 (s, 4H), 6.76 (d, J = 148.2 Hz, 16H), 3.99 (m, 8H), 2.01 --1.71 (m, 8H), 1.70 --0.92 (m, 74H), 0.89 (d, J = 6.8 Hz, 12H). ¹³ C NMR (101 MHz, cdcl ₃ ) δ 157.99, 149.51, 139.93, 136.56, 131.59, 128.12, 126.09, 124.10, 122.78, 120.43, 68.35, 35.35, 32.08, 32.06, 29.86, 29.81, 29.78, 29.68, 29.57, 29.52, 26.28, 22.86, 14.29. HRMS (ESI, positive) m / z calcd for C ₉₀ H ₁₁₀ O ₄ [M] ⁺ 1254.8404, found 1254.8389 (see Figures 22A and 22B for NMR spectra).

706c (45 mg, 45%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 8.23 (s, 2H), 7.79 (s, 2H), 6.46 --6.94 (br, 8H), 3.92 --3.85 (m, 4H) ), 1.83 --1.78 (m, 2H), 1.63 (s, 9H), 1.52 --1.35 (m, 16H), 1.02 ^{--0.94 (m, 12H). 13} C NMR (126 MHz, CDCl ₃ ) δ 158.28, 149.49 , 139.96, 136.52, 131.59, 128.17, 126.12, 124.11, 122.77, 120.44, 70.96, 70.94, 39.59, 39.55, 35.35, 32.07, 30.75, 29.86, 29.33, 24.08, 23.31, 23.28, 14.33, 14.32, 11.32, 11.31.HR (ESI, positive) m / z calcd for C ₉₀ H ₁₁₀ O ₄ [M] ⁺ 1254.8404, found 1254.8389 (see Figures 24A and 24B for NMR spectra).

706d (49 mg, 49%) ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.23 (s, 4H), 7.80 (s, 4H), 6.85 (br, 16H), 4.12 --3.87 (m, 8H), 1.97 --1.74 (m, 8H), 1.74 --1.19 (m, 42H), 1.05 ^{--0.85 (m, 12H). 13} C NMR (100 MHz, cdcl ₃ ) δ 157.99, 149.51, 139.93, 136.56, 131.59, 128.12, 126.09 , 124.10, 122.79, 120.43, 68.34, 35.34, 32.06, 31.86, 29.53, 25.95, 22.83, 14.26 (see Figure 51 for NMR spectra).

Synthesis of compound 104b:
Solution of biphenyl-2,2'-ditrifluoromethanesulfonate (2.25 g, 5 mmol, 1.0 eq) and terminal alkyne (2.54 g, 11 mmol, 2.2 eq) dissolved in Et _{3 N (30 mL) and DMF (50 mL) 2} Cl ₂ (35 mg, 0.05 mmol) of Pd (PPh ₃ ) and CuI (19 mg, 0.1 mmol) were added to the mixture. The resulting mixture was refluxed overnight in an _{N 2 atmosphere.} The solvent was removed under reduced pressure and the residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give the corresponding compound 104b (2.38 g, 78%) as a yellow oil. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.68 (d, J = 7.2 Hz, 2H), 7.59 (d, J = 7.7 Hz, 2H), 7.52 (t, J = 7.4 Hz, 2H), 7.47 (d , J = 7.3 Hz, 1H), 7.31 (t, J = 7.7 Hz, 1H), 7.17 (d, J = 8.7 Hz, 4H), 6.82 (d, J = 8.7 Hz, 4H), 3.84 (d, J = 5.4 Hz, 4H), 1.77 --1.71 (m, 2H), 1.59 --1.28 (m, 17H), 0.96 (m, 12H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.53, 145.88, 139.47, 132.89 , 131.50, 130.57, 127.52, 127.41, 127.11, 123.65, 115.16, 114.55, 93.26, 87.73, 70.63, 39.42, 30.61, 29.18, 23.95, 23.16, 14.21, 11.21. HRMS (ESI, positive) m / z calcd for C ₄₄ H ₅₀ O ₂ [M] ⁺ 610.3811, found 610.3814.

Synthesis of compound 106b:
Compound 104b (61 mg, 0.1 mmol) was dissolved in _{150 mL anhydrous CH 2} Cl _{2 in a 250 mL heat-dried flask.} Trifluoroacetic acid (0.1 mL, 1.3 mmol) was added and the reaction was stirred under nitrogen. After stirring at room temperature for 1 hour, the reactants were _{cooled with saturated LVDS 3} solution (5.0 _{mL), washed with H 2} O (2 x 30 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give the corresponding compound 106b (60 mg, 98%) as a yellow oil. ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 10.54 (d, J = 8.5 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 8.00 --7.96 (m, 1H), 7.87 (d, J = 7.3 Hz, 1H), 7.73 (t, J = 7.3 Hz, 1H), 7.69 --7.64 (m, 3H), 7.60 (m, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.09 (d, J = 8.5 Hz, 2H), 7.00 (d, J = 8.7 Hz, 2H), 4.01 --3.90 (m, 4H), 1.87 --1.77 (m, 2H), 1.64 --1.36 (m, 16H), 1.11 --0.88 (m, 12H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159. 69, 158.96, 139.10, 134.40, 132. 79, 132.75, 132.63, 132.36, 131.24, 131.02, 129.30, 129.25, 127.92, 126.70, 126.52 , 125.78, 125.58, 119.53, 115.59, 114.81, 114.39, 95.23, 91.11, 70.66, 70.61, 39.50, 39.39, 30.64, 30.56, 29.18, 29.13, 23.97, 23.90, 23.14, 23.10, 14.17, 14.14, 11.22, 11.17. HRMS (ESI, positive) m / z calcd for C ₄₄ H ₅₀ O ₂ [M] ⁺ 610.3811, found 610.3807.

Synthesis of compound 108b:
Use of MSA: Compound 104b (61 mg, 0.1 mmol) was dissolved in _{150 mL anhydrous CH 2} Cl _{2 in a 250 mL heat-dried flask.} Methanesulfonic acid (0.065 mL, 1.0 mmol) was added dropwise under nitrogen at 0 ° C., and the reaction was then warmed to room temperature. After stirring at room temperature for 3 hours, the reactants were _{cooled with saturated LVDS 3} solution (5.0 _{mL), washed with H 2} O (2 x 30 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give the corresponding compound 108b (52 mg, 85%) as a yellow oil.

Step c:
Use of TFA-TfOH: Compound 104b (61 mg, 0.1 mmol) was dissolved in _{150 mL anhydrous CH 2} Cl _{2 in a 250 mL heat-dried flask.} Trifluoroacetic acid (0.1 mL, 1.3 mmol) was added and the reaction was stirred under nitrogen. After stirring at room temperature for 1 hour (TLC showed no residue of 104b), the reaction was cooled to −40 ° C. and 5 drops of trifluic acid was added to the reaction mixture. The color immediately changed to dark blue. _{The reaction is cooled with a saturated LVDS 3} solution (5.0 mL), the solution is slowly warmed to room temperature, then _{washed with H 2} O (2 x 30 mL) and dried, while the TLC shows no residue of the intermediate compound. (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give the corresponding compound 108b (55 mg, 90%) as a yellow oil. ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 8.29 (d, J = 7.9 Hz, 2H), 8.20 (d, J = 7.6 Hz, 2H), 8.07 --8.03 (m, 3H), 7.92 (t, J = 7.9 Hz, 1H), 7.62 (d, J = 8.6 Hz, 4H), 7.14 (d, J = 8.6 Hz, 4H), 4.03 --3.97 (m, 4H), 1.85 (m, 2H), 1.62 --1.40 ( m, 16H), 1.01 (m, 12H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.14, 139.58, 133.20, 131.28, 131.13, 130.95, 127.72, 126.41, 125.57, 124.86, 124.24, 123.73, 114.59, 70.77 , 39.65, 30.78, 29.32, 24.11, 23.27, 14.30, 11.35. HRMS (ESI, positive) m / z calcd for C ₄₄ H ₅₀ O ₂ [M] ⁺ 610.3811, found 610.3803.

Synthesis of compound 1602:
A solution of 4-bromo-2,6-diiodaniline (1600, 4.24 g, 10.0 mmol) dissolved in 20.0 mL of 6M HCl was dissolved in 5 mL of cold water while cooling in an ice bath, and NaNO ₂ (0.83 g, 0.83 g, 12.0 mmol) The solution was added dropwise. The resulting diazonium salt solution was stirred at 0 ° C. for 30 minutes before the solution _{was dissolved in 1: 2 CH 3} CN / water (30 mL) with diethylamine (1.83 g, 25.0 mmol) and K ₂ CO ₃ (6.9 g). , 50.0 mmol). The reaction mixture was then stirred at 0 ° C. for 30 minutes _{and extracted with CH 2} Cl ₂ (2 x 50 mL). The organic layer was then washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated by evaporation. The crude product was purified by column chromatography (SiO ₂ , hexane / DCM) to give the pure product 1602 (3.3 g, 65% yield) as a brown oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.97 (s, 2H), 3.76 (q, J = 7.2 Hz, 4H), 1.36 --1.29 (m, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 151.60, 141.20, 118.33, 91.72, 49.44, 42.15, 15.23, 11.68. HRMS (TOFMS) calcd for C ₁₀ H ₁₂ BrI ₂ N ₃ [M] ⁺ 506.8304, found 506.8297 (See Figures 29A and 29B for NMR spectra) ..

Synthesis of Compound 1604: _{Compound 1602 (2.54 g, 5 mmol, 1.0 eq) dissolved in Et 3} N (30 mL) and THF (60 mL) and terminal Alkin H-CC-Ph-4-OiBu (2.54 g, 11 mmol, 2.2 eq) ), Pd (PPh ₃ ) ₂ Cl ₂ (35 mg, 0.05 mmol) and CuI (19 mg, 0.1 mmol) were added. The resulting mixture was stirred overnight in an _{N 2 atmosphere at room temperature.} The ammonium salt was then removed by filtration. The solvent was removed under reduced pressure and the residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give the corresponding product 1604 (3.2 g, 90%) as a brown oil. ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.58 (s, 2H), 7.38 --7.35 (m, 4H), 6.86 --6.84 (m, 4H), 3.86 --3.80 (m, 8H), 1.72 (m, 2H) ), 1.47 (m, 9H), 1.36 --1.28 (m, 16H), 0.94 ^{--0.91 (m, 9H). 13} C NMR (126 MHz, CDCl ₃ ) δ 159.62, 152.81, 135.11, 133.01, 118.80, 116.38, 115.37, 114.66, 93.68, 85.65, 70.73, 39.49, 30.65, 29.22, 23.99, 23.18, 14.22, 11.25. HRMS (TOFMS) calcd for C ₄₂ H ₅₄ BrN ₃ O ₂ [M] ⁺ 711.3399, found 711.3393 (About NMR spectrum) See Figures 30A and 30B).

Synthesis of Compound 1606: Triazene 1604 (1.43 g, 2.0 mmol) was dissolved in iodomethane (20.0 mL) and the solution was heated at 130 ° C. for 24 hours in a sealed thick tube. The reaction mixture was cooled and the solvent was evaporated to dryness. The residue was then _{dissolved in CH 2} Cl ₂ and the solution was filtered through a short plug of silica gel. After evaporation, the crude product was purified by column chromatography (SiO ₂ , hexane / DCM) to give iodide 1606 (1.26 g, 85%) as a yellow oil. ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.55 (d, J = 8.8 Hz, 2H), 7.53 (s, 1H), 6.91 (d, J = 8.9 Hz, 2H), 3.91 --3.85 (m, 2H) , 1.75 (m, 1H), 1.58 --1.42 (m, 4H), 1.35 (m, 4H), 0.98 ^{--0.91 (m, 6H). 13} C NMR (126 MHz, CDCl ₃ ) δ 160.22, 133.32, 133.27, 132.99, 121.40, 114.77, 114.26, 105.81, 95.00, 89.94, 70.71, 39.44, 30.63, 29.21, 23.97, 23.18, 14.24, 11.26. HRMS (TOFMS) calcd for C ₃₈ H ₄₄ BrIO ₂ [M] ⁺ 738.1569, found 738.1561 (See Figures 31A and 31B for NMR spectra).

Synthesis of Compound 1608: A solution of n-butyllithium dissolved in hexane (0.6 mL, 1.5 mmol, 2.5) in a solution of aryl iodide 1606 (1.11 g, 1.5 mmol, 1.0 eq) in THF (20 mL) at −78 ° C. M, 1.0 equivalent) was added. After stirring at −78 ° C. for 30 minutes, trimethyl borate (0.16 g, 1.5 mmol, 1.0 eq) was added; the reaction was removed from the cooling tank and warmed. At room temperature, the reaction was cooled by adding 2N HCl and then extracted with DCM. The extract was washed with water, dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. The crude residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give arylboronic acid 1608 (0.76 g, 77%) as a yellow oil. ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.67 (s, 1H), 7.47 (d, J = 8.7 Hz, 2H), 6.89 (d, J = 8.7 Hz, 2H), 6.56 (s, 1H), 3.87 (dd, J = 5.7, 1.7 Hz, 2H), 1.74 (dd, J = 12.2, 6.1 Hz, 1H), 1.53 --1.41 (m, 4H), 1.33 (m, 4H), 0.96 --0.91 (m, 6H) ). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 160.55, 135.10, 133.42, 129.77, 124.10, 114.96, 113.14, 95.89, 87.00, 77.41, 77.16, 76.90, 70.81, 39.45, 30.63, 29.21, 23.97, 23.18, 14.22 , 11.25. MALDI-TOF calcd for C ₃₈ H ₄₆ BBrO ₄ [M + K + H] ⁺ 696.2, found 696.7 (see Figures 32A and 32B for NMR spectra).

Synthesis of Compound 1610: Arylboronic acid 1608 (0.66 g, 1.0 mmol) and pinacol (0.14 g, 1.2 mmol) were dissolved in toluene (20.0 mL) and the solution was heated at 120 ° C. for 2 hours. The solvent was evaporated to dryness and the residue was purified by flash column chromatography (SiO ₂ , hexane / DCM) to give monomer 1610 (0.69 g, 94%) as yellow oil, which solidified when left to stand. ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.56 (s, 1H), 7.43 (d, J = 8.9 Hz, 2H), 6.85 (d, J = 8.9 Hz, 2H), 3.81 (d, J = 5.8 Hz) , 2H), 1.73- 1.67 (m, 1H), 1.45 (m, 4H), 1.36 (s, 6H), 1.31 (m, 4H), 0.91 (m, 6H). ¹³ C NMR (126 MHz, CDCl ₃₎ ) δ 159.74, 159.73, 133.59, 133.01, 133.00, 128.88, 128.86, 122.72, 114.63, 114.62, 114.57, 114.56, 92.06, 86.83, 84.40, 84.39, 70.51, 70.50, 39.36, 39.35, 30.53, 29.12, 29.11 23.88, 23.07, 14.12, 11.17, 11.16. MALDI-TOF calcd for C ₄₄ H ₅₆ BBrO ₄ [M] ⁺ 738.3, found 738.7 (see Figures 33A and 33B for NMR spectra).

Synthesis of Polymer 1704c: Monomer 700c (100mg, 0.135 _{mmol) dissolved in toluene (8mL) in Schlenk tube, K 2} CO ₃ (2M / H2O, 1.5mL, 3 mmol), and Aliquat® 336 (1 drop). _{Pd (PPh 3} ) ₄ (4.5 mg, 0.004 mmol) was quickly added to the degassed solution of. The mixture was stirred at 120 ° C. for 3 days. Next, a degassed solution of bromobenzene (16 mg, 0.1 mmol) dissolved in toluene (0.5 mL) was added to the reaction mixture with a syringe, and the reaction was refluxed for an additional 12 hours. The solution was cooled to room temperature and precipitated in cooled methanol (200 mL). The resulting solid was collected by filtration and purified by column chromatography (SiO ₂ , hexane / DCM) to give the desired polymer 1704c (70 mg, 70%) as an orange solid. ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.32 (br, 1H), 7.48 (br, 2H), 6.83 (br, 2H), 3.79 (br, 2H), 1.69 (br, 1H), 1.35 (br, 8H), 0.90 (br, 6H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159.71, 141.77, 138.47, 134.75, 133.30, 133.22, 122.73, 115.24, 114.74, 114.63, 94.14, 88.06, 70.67, 39.44, 30.60 , 29.18, 23.93, 23.16, 14.20, 11.22 (see Figures 34A and 34B for NMR spectra).

Synthesis of nanostructures 1706c: Polymer 1704c (50.0 mg) was dissolved in _{200 mL anhydrous CH 2} Cl _{2 in a 250 mL heat-dried flask.} Trifluoroacetic acid (0.5 mL) was added to the degassed solution. After stirring at room temperature for 24 hours, the reaction was cooled to −40 ° C. and then 5 drops of trifluic acid were added. After 1 hour, the reactants were _{cooled with saturated LVDS 3} solution (5.0 mL), the solution was warmed to room temperature _{, washed with H 2} O (2 x 10 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was redissolved in CH ₂ Cl ₂ (1.0 mL) and precipitated in chilled methanol (200 mL). The resulting solid was collected by filtration, washed with methanol and dried under vacuum to give nanostructures 1706c as a black solid (47 mg, 94%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 8.42 --5.75 (br, 5H), 4.39 --3.13 (br, 2H), 2.56 --0.24 (br, 11H). ¹³ C NMR (126 MHz, CDCl ₃ ) δ 159 . 69, 159.13, 133.27, 130.32, 114.89, 107.77, 77.41, 77.16, 76.91, 70.81, 39.63, 34.18, 31.60, 30.76, 29.86, 29.37, 28.88, 28.14, 28.00, 26.04, 24.99, 24.07, 23.27, 14.30, 11.36 ..

^{Comparing the 1} H-NMR spectra of 104b, 106b, and 108b (see above for structure) (FIG. 41), the signal located around 10.5 ppm is a proton pointing towards the alkyne of the monocyclic product. The signal was abolished in the dicyclization product (pyrene derivative). Therefore, the appearance and disappearance of this signal can be a strong evidence of the efficiency of the alkyne aromatic cyclization reaction. Based on this, a small reaction was carried out in an NMR tube using deuterated trifluoroacetic acid (TFA-d) as a Lewis acid to facilitate the reaction. First, Polymer 8 (2 mg, 0.004 mmol (based on repeating unit molecular weight)) and CDCl3 (0.6 mL) were charged into an NMR tube. After complete dissolution, a first NMR test was performed on just the polymer. A second NMR test was performed immediately after the addition of TFA-d (15 μl, 0.2 mmol), and after a period of time to record the reaction, the following NMR tests were performed one by one (FIG. 42). The results showed that some new signals appeared, and after the addition of TFA-d, the signals became stronger in the 10.5 to 11.3 ppm region, indicating the formation of monocyclized products. Over time, these signals gradually weakened, but remained a little after 12 hours. Other similar reactions with more TFA (100 eq) were performed simultaneously, which disappeared after 12 hours. NMR of GNR-TFA showed a trace signal around 10.5 to 11.0 ppm. This means that most of the alkynes were involved in the cyclization reaction (Fig. 43). Comparing the polymer with ¹ H NMR of GNR, all peaks are relatively sharp before cyclization, which is due to the flexibility of the polymer (Fig. 44). After cyclization, the peak was wide and weak due to the rigidity of the GNR. This also showed the result of cyclization.

FIG. 45 separately provides partial IR spectra of polymer (blue), TFA-promoted polymer (red), MSA-promoted polymer (light blue), and TFA-TfOH-promoted polymer (green). To do. The yellow oval indicates the infrared absorption peak of the alkyne. Polymers showed strong absorption of alkynes in this region (blue), while polymers promoted by TFA and MSA showed weak absorption (red and light blue). The polymer promoted by TFA-TfOH showed no absorption of alkynes in this region. This indicated the absence of alkyne residues in this nanoribbon, confirming that TFA-TfOH promoted complete cyclization of alkynes.

As shown in FIG. 46, the intermolecular H ... H repulsion between the phenyl groups of the molecular skeleton causes a significant inclination of the latter with respect to the surface. The line profile pointing to the GNR (bottom of the corresponding STM image) shows that the distance between the two phenyl groups on the same side is about 1.25 nm before calibration. Using the HOPG atomized STM image as a reference, it was found that the distance between the two carbon atoms was 0.27 nm in HOPG. This is larger than the theoretical value (0.25 nm). According to this, the distance between the two phenyl groups on the same side is about 1.16 nm after calibration, which closely corresponds to the longitudinal length of the three repeating units (about 0.9 nm). An internal alkyl chain at the end of the GNR could also be observed (Fig. 47).

Synthesis of Compound C: To a solution of terminal Alkin compound B (1.85 g, 7.2 mmol) dissolved in THF (50 mL) at −78 ° C., add n-BuLi hexane solution (2.5 M, 2.8 mL, 7 mmol) under nitrogen. It was. After stirring at −78 ° C. for 30 minutes and then at 0 ° C. for 15 minutes, compound A (1.0 g, 2.4 mmol) was added to the resulting solution at 0 ° C. After stirring at room temperature for 16 hours, the reaction mixture was cooled with _{saturated NH 4} Cl and then extracted with _{CH 2} Cl _2. The organic layer was _{washed with H 2} O and brine and dried over Na ₂ SO ₄ . After evaporating the solvent, the residue _{was dissolved in CH 3} CN (100 mL). SnCl ₂ (1.3 g, 7 mmol) and 2 mL of water were added and the reaction was refluxed for 12 hours. After evaporation of the solvent, the residue was purified by column chromatography (SiO2, hexane / DCM) to give compound C (1.62 g, 75%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.55 --7.74 (m, 6H), 7.43 --7.39 (m, 4H), 7.01 (d, J = 8.4 Hz, 4H), 6.75 (d, J = 8.4 Hz, 4H), 3.92 (t, J = 6.6 Hz, 4H), 1.79 --1.73 (m, 4H), 1.45 --1.28 (m, 28H), 0.90 (t, J = 6.9 Hz, 6H). ¹³ C NMR (126) MHz, CDCl ₃ ) δ 159. 80, 145.53, 141.10, 133.22, 129.67, 128.20, 128.05, 126.71, 125.13, 114.56, 100.63, 87.62, 68.21, 32.04, 29.70, 29.69, 29.51, 29.46, 29.28, 26.13, 22.83, 14.27.

Synthesis of Compound D: B (155 mg, 0.6mmol ), C (180mg, 0.2mmol), PdCl 2 (PPh3) 2 (14.3mg, 0.02mmol), CuI (7.6mg, 0.04mmol), and PPh ₃ (10.4 _{Et 3} N (30 mL) was added to the mixture of mg, 0.04 mmol) under a nitrogen atmosphere. The resulting mixture was stirred at reflux temperature for 24 hours. After evaporation of Et ₃ N, the residue was purified by column chromatography (SiO ₂ , hexane / DCM) to give compound D (1.30 g, 52%). ^{1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.65 (d, J = 7.1 Hz, 4H), 7.54 --7.44 (m, 6H), 7.13 (d, J = 8.7 Hz, 8H), 6.76 (d, J = 8.7 Hz, 8H), 3.93 (t, J = 6.6 Hz, 8H), 1.79 --1.73 (m, 8H), 1.45 --1.26 (m, 56H), 0.88 (t, J = 6.8 Hz, 12H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 159. 49, 145.31, 139.51, 133.06, 130.50, 127.75, 127.60, 124.90, 115.43, 114.60, 98.70, 87.47, 68.22, 32.05, 29.72, 29.70, 29.53, 29.47, 29.32, 26.16 , 22.84, 14.27.

1-Bromo-4-tert-butylbenzene (213 mg, 1 mmol), 2,6-diynylphenylborate (1 mmol), and K ₂ CO ₃ (276 mg, 2 mmol) in THF (60 mL) and water (10 mL). Dissolved in solution. Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added to the solution and then the mixture was degassed by bubbling nitrogen for 30 minutes. The resulting mixture was _{stirred under an N 2} atmosphere at 80 ° C. for 24 hours. After the reaction was complete, the mixture was diluted with DCM _{, washed with H 2} O and dried over Na ₂ SO ₄ . The solvent was removed under reduced pressure and the residue was purified by column chromatography to give compound 902.

902a: 86% yield. ^{1 1} H NMR (500 MHz, cdcl ₃ ) δ 7.59 (s, 2H), 7.55 (d, J = 8.3 Hz, 2H), 7.50 (d, J = 8.3 Hz, 2H), 7.13 ( d, J = 8.7 Hz, 4H), 6.78 (d, J = 8.7 Hz, 4H), 3.79 (s, 6H), 1.44 (s, 9H), 1.40 (s, 9H). ¹³ C NMR (125 MHz, cdcl ₃ ) δ 159. 59, 150.07, 149.92, 143.60, 136.56, 133.24, 132.95, 130.31, 128.71, 124.28, 123.18, 115.75, 114.17, 113.93, 92.40, 88.72, 55.40, 34.81, 34.68, 31.65, 31.33.

902b: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 7.60 (s, 2H), 7.57 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.13 (d, J = 8.7 Hz, 4H), 6.78 (d, J = 8.8 Hz, 4H), 3.94 (t, J = 6.5 Hz, 4H), 1.81 --1.75 (m, 4H), 1.45 (s, 9H), 1.42 (s, 9H), 1.36 (m, 12H), 0.93 (t, J = 6.1 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 19, 150.02, 149.87, 143.58, 136.59, 132.92, 130.32, 128.63 , 124.26, 123.22, 115.47, 114.45, 92.53, 88.64, 68.15, 34.80, 34.67, 31.71, 31.65, 31.32, 29.30, 25.83, 22.74, 14.17.

902c: ^{1 1} H NMR (400 MHz, cdcl3) δ 7.61 (s, 2H), 7.58 (d, J = 8.6 Hz, 2H), 7.53 (d, J = 8.6 Hz, 2H), 7.14 (d, J = 8.9) Hz, 4H), 6.79 (d, J = 8.9 Hz, 4H), 3.94 (t, J = 6.6 Hz, 4H), 1.82 --1.75 (m, 4H), 1.39 (dd, J = 47.3, 14.7 Hz, 46H) ), 0.93 (t, J = 6.9 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 16, 149.98, 149.84, 143.57, 136.58, 132.90, 130.33, 128.60, 124.25, 123.22, 115.45, 114.42 , 92.53, 88.63, 68.11, 34.78, 34.65, 32.05, 31.65, 31.31, 29.72, 29.70, 29.53, 29.47, 29.33, 26.15, 22.84, 14.28.

902': In a 100 mL heat-dried flask, compound 900 (53 mg, 0.1 mmol) was dissolved in _{50 mL anhydrous CH 2} Cl _2. Trifluoroacetic acid (570 mg, 5 mmol) was added and the reaction was stirred under nitrogen. After stirring at room temperature for 1 hour (TLC showed no residue 900), the reactants were _{cooled with saturated acrylamide 3} aqueous solution (5 mL). The solution was then _{washed with H 2} O (2 x 30 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography (SiO ₂ , DCM) to give compound 902'(52 mg, 99%) as a yellow solid. ¹ H NMR (400 MHz, cdcl ₃ ) δ 10.37 (d, J = 9.0 Hz, 1H), 8.00 (d, J = 2.2 Hz, 1H), 7.98 (d, J = 2.2 Hz, 1H), 7.83 (d) , J = 2.2 Hz, 1H), 7.75 (dd, J = 9.0, 2.2 Hz, 1H), 7.70 --7.77 (m, 2H), 7.64 (s, 1H), 7.53 --7.49 (m, 2H), 7.10- 7.05 (m, 2H), 7.02 --6.98 (m, 2H), 3.93 (s, 3H), 3.89 (s, 3H), 1.48 (s, 9H), 1.38 (s, 9H). ¹³ C NMR (126 MHz) , cdcl ₃ ) δ 159. 86, 159.07, 149.10, 148.20, 139.17, 133.44, 133.23, 132.99, 132.73, 132.62, 132.01, 131.27, 131.17, 129.09, 128.41, 127.20, 126.12, 125.80, 123.81, 122.63, 118. , 114.36, 114.16, 113.95, 113.83, 94.24, 91.84, 55.51, 55.48, 35.03, 34.67, 31.47, 31.43.

904a: In a 200 mL heat-dried flask, 902'(52 mg, 0.1 mmol) was dissolved in _{100 mL anhydrous CH 2} Cl _2. When a drop of trifluic acid was added to the reaction mixture at 0 ° C., the color of the solution immediately changed to dark blue. After stirring at 0 ° C. for 15 minutes, the reactants were _{cooled with saturated acrylamide 3} aqueous solution (5 mL). The solution was then _{washed with H 2} O (2 x 30 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography (SiO ₂ , hexane / DCM 3: 1) to give the corresponding compound 904a (27 mg, 52%) as a yellow solid. Single crystals were obtained by slowly evaporating at room temperature and recrystallizing a solution of 904a in chloroform and methanol. ^{1 1} H NMR (500 MHz, cdcl ₃ ) δ 8.30 (s, 2H), 8.19 (s, 2H), 7.98 (s, 2H), 7.64 (d, J = 8.7 Hz, 4H), 7.13 (d, J = 8.7 Hz, 4H), 3.96 (s, 6H), 1.59 (s, 9H), 1.39 (s, 9H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 15, 149.16, 148.06, 139.44, 133.84, 131.28, 130.58, 130.54, 127.91, 123.71, 121.95, 121.24, 113.95, 55.53, 35.60, 35.36, 32.09, 31.95.

One-step synthesis of compound 904: Compound 900 (0.1 mmol) was dissolved in _{50 mL anhydrous CH 2} Cl _{2 in a 100 mL heat-dried flask.} Trifluoroacetic acid (570 mg, 5 mmol) was added and the reaction was stirred under nitrogen. After stirring at room temperature for 1 hour (TLC showed no residue 1), the reaction was cooled to 0 ° C. and then a drop of trifluic acid was added. After stirring at 0 ° C. for 15 minutes, the reactants were _{cooled with saturated acrylamide 3} aqueous solution (5 mL). The solution was then _{washed with H 2} O (2 x 30 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography (SiO ₂ , hexane / DCM 3: 1) to give the corresponding compound 904.

904b: ¹ H NMR (400 MHz, cdcl ₃ ) δ 8.34 (s, 2H), 8.21 (s, 2H), 8.01 (s, 2H), 7.65 (d, J = 8.6 Hz, 4H), 7.13 (d, J = 8.7 Hz, 4H), 4.12 (t, J = 6.6 Hz, 4H), 1.94 --1.86 (m, 4H), 1.61 (s, 9H), 1.58 --1.40 (m, 21H), 1.00 --0.94 (m) , 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 158. 73, 149.11, 148.02, 139.53, 133.63, 131.24, 130.61, 130.55, 127.87, 123.73, 121.96, 121.90, 121.27, 114.51, 68.29, 35.60, 35.35 , 32.09, 31.96, 31.84, 29.55, 26.00, 22.82, 14.24.

904c: ¹ H NMR (400 MHz, cdcl ₃ ) δ 8.32 (s, 2H), 8.19 (s, 2H), 7.99 (s, 2H), 7.63 (d, J = 8.7 Hz, 4H), 7.12 (d, J = 8.8 Hz, 4H), 4.11 (t, J = 6.6 Hz, 4H), 1.96 --1.81 (m, 4H), 1.59 (s, 9H), 1.53 --1.09 (m, 37H), 0.92 (t, J) = 6.8 Hz, 6H). ¹³ C NMR (101 MHz, cdcl ₃ ) δ 158. 73, 149.11, 148.02, 139.52, 133.63, 131.24, 130.61, 130.55, 129.53, 127.87, 123.72, 121.90, 121.27, 114.51, 68.31, 35.60, 35.35, 32.09, 31.96, 29.80, 29.77, 29.65, 29.60, 29.52, 26.33, 22.87, 14.30.

Compound 1000 was prepared as described for Compound 900, using Compound 1000'and 2-bromopyrene as starting materials.

1000a: ¹ H NMR (400 MHz, cdcl ₃ ) δ 8.54 (s, 2H), 8.27 (s, 2H), 8.12 (m, 4H), 7.73 (s, 2H), 7.00 (d, J = 8.9 Hz, 4H), 6.62 (d, J = 9.0 Hz, 4H), 3.69 (s, 6H), 1.64 (s, 9H), 1.48 (s, 9H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 53 , 150.36, 149.13, 142.82, 136.39, 132.88, 131.40, 130.29, 129.42, 127.78, 127.58, 127.53, 124.11, 123.59, 123.21, 122.17, 115.35, 113.92, 92.40, 88.64, 55.28, 35.43, 34.78, 32.14, 31.36.

1000b: ¹ H NMR (400 MHz, cdcl ₃ ) δ 8.59 (s, 2H), 8.30 (s, 2H), 8.14 (m, 4H), 7.77 (s, 2H), 7.02 (d, J = 8.9 Hz, 4H), 6.63 (d, J = 8.9 Hz, 4H), 3.83 (t, J = 6.6 Hz, 4H), 1.83 --1.59 (m, 13H), 1.54 --1.44 (m, 9H), 1.35 (m, 12H) ), 0.91 (t, J = 6.9 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 13, 150.32, 149.09, 142.77, 136.41, 132.84, 131.39, 130.28, 129.35, 127.79, 127.61, 127.51 , 124.10, 123.64, 123.21, 122.15, 115.06, 114.43, 92.55, 88.57, 68.02, 35.40, 34.76, 32.13, 31.65, 31.36, 29.20, 25.75, 22.69, 14.14.

1000c: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.61 (s, 2H), 8.14 (m, 7H), 7.75 (s, 2H), 7.00 (d, J = 8.7 Hz, 4H), 6.62 (d, J = 8.7 Hz, 4H), 3.82 (t, J = 6.5 Hz, 4H), 1.74 --1.63 (m, 4H), 1.53 --1.25 (m, 37H), 0.91 (t, J = 6.9 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 17, 150.41, 142.61, 136.80, 132.85, 131.56, 130.48, 129.40, 127.90, 127.80, 127.33, 125.93, 124.98, 124.90, 124.16, 123.65, 115.04, 114.44, 92.59 , 88.52, 68.05, 34.77, 32.03, 31.75, 31.36, 29.67, 29.48, 29.45, 29.25, 26.08, 22.82, 14.26.

1002a: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 11.17 (s, 1H), 8.25 (d, J = 1.7 Hz, 1H), 8.23 --8.16 (m, 4H), 8.08 (d, J = 9.0 Hz, 1H), 8.03 (d, J = 2.2 Hz, 1H), 7.90 (s, 1H), 7.80 (m, 3H), 7.46 (d, J = 8.7 Hz, 2H), 7.08 --7.03 (m, 4H), 3.95 (s, 3H), 3.91 (s, 3H), 1.64 (s, 9H), 1.60 (s, 9H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 92, 158.93, 149.36, 148.96, 138.55 , 138.15, 133.02, 132.84, 132.45, 131.63, 131.06, 130.61, 130.20, 129.77, 128.89, 128.50, 128.12, 128.07, 127.64, 127.21, 126.39, 125.41, 124.72, 124.46, 123.55, 122.99, 122.43, 121.90, 11 , 114.43, 114.42, 94.46, 92.07, 55.45, 55.44, 35.29, 34.78, 32.01, 31.46.

1002c:. FTIR (neat) cm -1 1 H NMR (400 MHz, cdcl 3) δ 11.13 (s, 1H), 8.17 (dd, J = 9.2, 4.5 Hz, 2H), 8.11 (q, J = 6.7 Hz , 3H), 8.03 (d, J = 9.0 Hz, 1H), 7.99 --7.95 (m, 2H), 7.84 (s, 1H), 7.74 (dd, J = 11.5, 9.1 Hz, 3H), 7.39 (d, J = 8.7 Hz, 2H), 7.01 (dd, J = 8.7, 1.7 Hz, 4H), 4.06 (m, 4H), 1.89 --1.82 (m, 4H), 1.53 (s, 12H), 1.40 --1.26 (m) , 25H), 0.90 (t, J = 6.8 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 61, 158.57, 149.14, 138.66, 137.97, 133.04, 132.90, 132.51, 131.82, 131.25, 130.80 , 130.18, 129.98, 128.98, 128.69, 128.18, 127.82, 127.57, 127.53, 126.50, 126.22, 125.40, 125.09, 124.82, 124.73, 124.55, 124.54, 123.76, 119.83, 115.84, 115.09, 115.01, 94.64, 91.88, 68. , 32.09, 32.07, 31.48, 29.86, 29.79, 29.76, 29.74, 29.65, 29.59, 29.56, 29.52, 29.50, 29.42, 26.30, 26.23, 22.86, 14.29.

1004a: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.34 (s, 2H), 8.25 (d, J = 9.4 Hz, 2H), 8.21 (s, 4H), 7.77 (d, J = 9.5 Hz, 2H) , 7.48 (d, J = 8.6 Hz, 4H), 7.05 (d, J = 8.7 Hz, 4H), 3.95 (s, 6H), 1.64 (s, 9H), 1.59 (s, 9H). ¹³ C NMR ( 100 MHz, cdcl ₃ ) δ 158. 92, 149.75, 149.27, 139.29, 138.71, 133.07, 131.14, 131.01, 130.83, 130.29, 128.28, 125.97, 125.56, 124.83, 124.63, 124.43, 122.60, 122.47, 121.70, 114.51, 55.56 , 35.35, 35.30, 32.05, 31.48.

1004b: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.35 (s, 2H), 8.28 (d, J = 9.4 Hz, 2H), 8.22 (d, J = 1.1 Hz, 4H), 7.78 (d, J = 9.5 Hz, 2H), 7.46 (d, J = 8.7 Hz, 4H), 7.04 (d, J = 8.7 Hz, 4H), 4.10 (t, J = 6.6 Hz, 4H), 1.89 (m, 4H), 1.65 (s, 9H), 1.60 (s, 9H), 1.57 --1.32 (m, 12H), 0.98 (t, J = 7.1 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 158. 49, 149.71 , 149.23, 139.38, 138.50, 131.10, 131.03, 130.84, 130.25, 128.33, 125.99, 125.57, 124.86, 124.59, 124.42, 122.69, 122.55, 122.43, 121.68, 115.11, 68.32, 35.34, 35.29, 32.05, 31.86, 29. , 22.82, 14.26.

1004c: ¹ H NMR (400 MHz, cdcl ₃ ) δ 8.34 (s, 2H), 8.30 (d, J = 9.4 Hz, 2H), 8.21 (s, 2H), 8.16 (d, J = 7.6 Hz, 2H) , 8.01 (dd, J = 8.0, 7.1 Hz, 1H), 7.77 (d, J = 9.5 Hz, 2H), 7.45 (d, J = 8.7 Hz, 4H), 7.03 (d, J = 8.7 Hz, 4H) , 4.09 (t, J = 6.6 Hz, 4H), 1.94 --1.84 (m, 4H), 1.63 (s, 9H), 1.55 --1.26 (m, 28H), 0.91 (t, J = 6.9 Hz, 6H). ¹³ C NMR (101 MHz, cdcl ₃ ) δ 158. 51, 149.85, 139.38, 138.46, 131.23, 131.04, 130.98, 130.24, 128.36, 126.13, 126.08, 125.67, 125.15, 124.93, 124.53, 124.46, 124.34, 122.64, 121.58 , 115.14, 68.35, 35.37, 32.09, 32.05, 29.80, 29.77, 29.67, 29.58, 29.52, 26.31, 22.87, 14.30.

Compound 1100: 2,7-dibromopyrene (360 mg, 1 mmol), 2,6-diynylphenylborate (2.5 mmol), and K ₂ CO ₃ (552 mg, 4 mmol) in toluene (80 mL) and water (20 mL). Dissolved in solution. Pd (PPh ₃ ) ₄ (116 mg, 0.1 mmol) was added to the solution and then the mixture was degassed by bubbling nitrogen for 30 minutes. The resulting mixture was _{stirred under an N 2} atmosphere at 80 ° C. for 48 hours. After the reaction was complete, the mixture was diluted with DCM _{, washed with H 2} O and dried over Na ₂ SO ₄ . The solvent was removed under reduced pressure and the residue was purified by column chromatography to give compound 1100.

1100a: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.63 (s, 4H), 8.20 (s, 4H), 7.76 (s, 4H), 7.03 (d, J = 8.9 Hz, 8H), 6.61 (d, J = 8.9 Hz, 8H), 3.76 (t, J = 6.6 Hz, 8H), 1.67 (m, 8H), 1.50 (s, 18H), 1.39 --1.23 (m, 24H), 0.87 (t, J = 6.9) Hz, 12H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 159. 21, 150.39, 142.62, 136.69, 132.86, 130.74, 129.42, 127.72, 127.64, 124.33, 123.65, 114.98, 114.51, 92.69, 88.63, 68.02, 34.79, 31.65, 31.37, 29.19, 25.72, 22.68, 14.13.

1100b: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.60 (s, 4H), 8.17 (s, 4H), 7.73 (s, 4H), 7.00 (d, J = 8.9 Hz, 8H), 6.58 (d, J = 9.0 Hz, 8H), 3.74 (t, J = 6.6 Hz, 8H), 1.69 --1.58 (m, 8H), 1.51 (s, 18H), 1.41 --1.09 (m, 56H), 0.87 (t, J) = 6.9 Hz, 12H). ¹³ C NMR (101 MHz, cdcl ₃ ) δ 159. 22, 150.39, 142.62, 136.69, 132.87, 130.74, 129.42, 127.72, 127.64, 124.33, 123.65, 114.99, 114.52, 92.69, 88.63, 68.05, 34.80, 32.03, 31.38, 29.68, 29.67, 29.49, 29.45, 29.25, 26.07, 22.82, 14.26.

In a 100 mL heat-dried flask, compound 1100b (0.1 mmol) was dissolved in _{80 mL anhydrous CH 2} Cl _2. Trifluoroacetic acid (570 mg, 5 mmol) was added and the reaction was stirred under nitrogen. After stirring at room temperature for 1 hour, the reaction mixture _{was cooled with saturated LVDS 3} solution (15 mL). The solution was then _{washed with H 2} O (2 x 50 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography (SiO ₂ , DCM) to give a mixture of compounds 1102b and 1104b (148 mg, 99%) as a yellow oil. ¹ H NMR (500 MHz, cdcl ₃ ) δ 11.03 (s, 1H), 11.00 (s, 2H), 8.21 (d, J = 9.4 Hz, 1H), 8.13 (s, 2H), 8.09 (d, J = 2.1 Hz, 2H), 8.06 (d, J = 2.1 Hz, 1H), 7.95 --7.92 (m, 3H), 7.89 (s, 2H), 7.79 (d, J = 5.6 Hz, 3H), 7.71 --7.68 ( m, 3H), 7.61 --7.57 (m, 2H), 7.43 (d, J = 8.7 Hz, 2H), 7.38 --7.33 (m, 3H), 7.03 --6.89 (m, 11H), 4.07 (t, J = 6.6 Hz, 5H), 4.00 --3.94 (m, 5H), 1.93 --1.75 (m, 13H), 1.56 --1.26 (m, 110H), 0.95 ^{--0.88 (m, 24H). 13} C NMR (101 MHz, cdcl) ₃ ) δ 159. 58, 159.55, 158.59, 158.51, 149.11, 148.99, 138.72, 137.93, 137.48, 133.05, 133.00, 132.84, 132.68, 132. 53, 131.22, 131.01, 130.24, 130.21, 130.14, 129.46, 128.98, 128.58 , 128.47, 127.97, 127.38, 127.32, 126.34, 126.27, 125.67, 125.34, 124.57, 124.51, 123.60, 119.90, 119.78, 115.86, 115.74, 114.99, 114.95, 94.57, 94.52, 91.87, 91.75, 68.33, 34.81, 32. , 31.49, 31.47, 29.85, 29.81, 29.77, 29.75, 29.68, 29.65, 29.61, 29.58, 29.54, 29.51, 29.44, 26.34, 26.31, 26.24, 26.23, 22.86, 14.29 (See Figure 53 for the X-ray image of compound 1102b. reference).

Compound 1100 (0.1 mmol) was dissolved in _{80 mL anhydrous CH 2} Cl ₂ in a 100 mL heat-dried flask. Trifluoroacetic acid (570 mg, 5 mmol) was added and the reaction was stirred under nitrogen at room temperature for 1 hour. The solution was slowly added to a pre-cooled 0 ° C. CH ₂ Cl ₂ (50 mL) trifluic acid (2 eq) solution. After stirring at 0 ° C. for 30 minutes, the reactants were _{cooled with saturated LVDS 3} solution (20 _{mL), washed with H 2} O (2 x 50 mL) and dried (Na ₂ SO ₄ ). After removing the solvent under reduced pressure, the residue was purified by column chromatography to give compound 1106 as a crimson solid.

1106a: ^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.30 (s, 4H), 8.14 (s, 4H), 8.10 (s, 4H), 7.41 (d, J = 8.7 Hz, 8H), 6.95 (d, J = 8.8 Hz, 8H), 4.05 (t, J = 6.6 Hz, 8H), 1.91 --1.79 (m, 8H), 1.62 (s, 18H), 1.56 --1.48 (m, 8H), 1.39 (m, 16H) ), 0.94 (t, J = 7.1 Hz, 12H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 158. 38, 149.75, 139.35, 138.19, 131.36, 131.19, 130.07, 126.05, 125.73, 125.46, 124.75, 124.51 , 122.52, 121.47, 115.09, 68.28, 35.36, 32.05, 31.86, 29.56, 25.97, 22.82, 14.24.

1106b: ¹ H NMR (400 MHz, toluene) δ 8.59 (s, 4H), 8.25 (s, 4H), 8.12 (s, 4H), 7.27 (d, J = 8.6 Hz, 8H), 6.82 (d, J = 8.7 Hz, 8H), 3.67 (t, J = 6.5 Hz, 8H), 1.74 --1.48 (m, 26H), 1.43 --1.18 (m, 56H), 0.92 (t, J = 6.8 Hz, 12H). ¹³ C NMR (100 MHz, toluene) δ 159.01, 149.75, 140.10, 138.60, 132.09, 131.90, 130.55, 126.95, 126.49, 126.27, 125.95, 125.40, 122.94, 122.36, 115.34, 68.05, 53.40, 35.45, 32.58, 32.18, 30.35 , 30.31, 30.21, 30.07, 30.05, 26.74, 23.34, 14.54 (see Figure 54).

^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 7.50 (s, 2H), 7.19 (d, J = 3.6 Hz, 2H), 6.71 (dt, J = 3.5, 0.8 Hz, 2H), 2.82 (t, J = 7.6 Hz, 4H), 1.70 (dt, J = 15.2, 7.4 Hz, 4H), 1.54 --1.17 (m, 21H), 1.01 ^{--0.83 (m, 6H). 13} C NMR (100 MHz, cdcl ₃ ) δ 150 . 19, 149.22, 132.65, 129.85, 125.89, 124.60, 124.46, 120.09, 91.59, 87.46, 34.66, 31.66, 31.64, 31.09, 30.39, 28.84, 22.70, 14.21.

^{1 1} H NMR (400 MHz, CDCl3) δ 7.49 (s, 2H), 7.10 (d, J = 3.6 Hz, 2H), 6.67 (d, J = 3.6 Hz, 2H), 2.80 (t, J = 7.5 Hz, 4H), 1.74 ―― 1.64 (m, 4H), 1.57 ―― 1.17 (m, 33H), 0.91 (t, J = 6.9 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 152. 29, 148.21, 131.88, 128.75, 126.55, 124.19, 120.86, 93.05, 84.36, 83.89, 34.71, 31.61, 31.55, 31.03, 30.28, 28.76, 25.14, 22.65, 14.15.

^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.51 (s, 2H), 8.27 (s, 2H), 8.13 (m, 4H), 7.71 (s, 2H), 6.66 (d, J = 3.6 Hz, 2H) , 6.46 (d, J = 3.6 Hz, 2H), 2.64 (t, J = 7.6 Hz, 4H), 1.64 (s, 9H), 1.36 (d, J = 83.2 Hz, 34H), 0.88 (t, J = 6.8 Hz, 6H). ¹³ C NMR (100 MHz, cdcl3) δ 150. 37, 149.04, 148.49, 142.51, 135.87, 131.87, 131.42, 130.37, 129.34, 127.97, 127.41, 127.35, 124.20, 124.15, 123.33, 123.16, 122.08, 120.41, 92.87, 86.35, 35.40, 34.79, 32.14, 31.61, 31.48, 31.32, 30.23, 28.74, 22.65, 14.19.

^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.57 (d, J = 9.4 Hz, 2H), 8.43 (s, 2H), 8.40 (s, 2H), 8.32 (s, 2H), 7.94 (d, J = 9.4 Hz, 2H), 7.06 (d, J = 3.4 Hz, 2H), 6.91 (d, J = 3.4 Hz, 2H), 2.98 (t, J = 7.4 Hz, 4H), 1.83 (m, 4H), 1.75 --1.59 (m, 18H), 1.57 --1.40 (m, 12H), 1.02 (t, J = 6.9 Hz, 6H). ¹³ C NMR (100 MHz, cdcl ₃ ) δ 149. 81, 149.27, 146.50, 145.17, 132.39, 131.90, 130.98, 130.75, 127.65, 126.17, 125.85, 125.25, 125.01, 124.89, 124.65, 124.49, 123.07, 122.62, 122.58, 122.39, 35.33, 35.30, 32.07, 32.01, 31.97, 31.87, 30.46, 28.89, 22. 14.37.

^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.54 (s, 4H), 8.18 (s, 4H), 7.70 (s, 4H), 6.67 (d, J = 3.6 Hz, 4H), 6.43 (d, J = 3.6 Hz, 4H), 2.59 (t, J = 7.5 Hz, 8H), 1.46 (s, 18H), 1.24 (m, 32H), 0.87 ^{--0.80 (m, 12H). 13} C NMR (100 MHz, cdcl ₃₎ ) δ 150. 39, 148.57, 142.42, 136.12, 131.95, 130.84, 129.37, 127.78, 127.33, 124.36, 124.17, 124.15, 123.35, 120.39, 92.93, 86.47, 34.81, 31.62, 31.49, 31.34, 30.24, 28.79, 22.67 14.17.

^{1 1} H NMR (400 MHz, cdcl ₃ ) δ 8.35 (s, 4H), 8.33 (s, 4H), 8.31 (s, 4H), 6.90 (d, J = 3.4 Hz, 4H), 6.81 (d, J = 3.4 Hz, 4H), 2.94 (t, J = 7.6 Hz, 8H), 1.81 --1.75 (m, 8H), 1.64 --1.61 (m, 18H), 1.50 --1.37 (m, 24H), 0.91 (m, 12H) ). 1 ¹³ C NMR (100 MHz, cdcl ₃ ) δ 149.95, 145.93, 144.68, 132.51, 132.00, 130.84, 126.21, 126.01, 125.50, 124.99, 124.87, 124.74, 124.45, 123.04, 122.09, 35.37, 32.01, 32.00, 31.83, 30.59, 29.06, 22.82, 14.30 (see Figure 52).

In view of the many feasible embodiments to which the principles of the present disclosure apply, the exemplary embodiments should be understood as merely preferred examples of disclosure, which limit the scope of the claimed invention. Should not be caught. Rather, the scope is defined by the following claims. Therefore, the Company claims all of the inventions that fall within the scope and purpose of these claims.

Claims (18)

A compound having a structure satisfying the following formula 1:
Equation 1
(In the formula, each R ¹ is independently selected from hydrogen, halogen, aliphatic, aryl, heteroaliphatic, or heteroaryl; each R ^a is independently aryl; aliphatic, alkoxy, amide, amine, thioether. , Haloalkyl, nitro, halo, silyl, alicyclic, and aryl substituted with one or more functional groups selected from aryl; or alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, silyloxy, And selected from electron donating groups selected from heteroaryls; each n is independently 1, 2, or 3; m is 1-1000). The compound according to claim 1, which has a structure satisfying any one or more of the following formulas 3 to 5.
Equation 3
Equation 4
Equation 5 The ^Ra group is substituted with one or more functional groups selected from aliphatic, alkoxy, amine, thioether, haloalkyl, nitro, halo, silyl, alicyclic, and aryl, and the one or more functional groups. The compound according to claim 1 or 2, wherein the substituent is located in meta, ortho, para, or a combination thereof with respect to the position where the ^{Ra group is bonded.} The compound according to any one of claims 1 to 3, wherein each ^Ra group is independently ^{substituted with a para functional group at the position where the Ra group is bonded.} The compound according to any one of claims 1 to 4, wherein each ^{Ra group is selected from the following.}
The compound according to any one of claims 1 to 5, wherein each R ^{1 is independently selected from hydrogen, alkyl, or a combination thereof.} The compound according to claim 6, wherein the alkyl is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, or a combination thereof. The compound according to claim 1, which is selected from the following.
The compound according to claim 1, wherein each R ¹ is independently selected from halogen or _{an aliphatic group terminalized with -SO 3} CH ₃ or -SO ₃ CF _3. The compound according to claim 1 or 2, which is selected from the following.
The compound according to any one of claims 1 to 10, which is axially asymmetric. A method comprising exposing the diyne precursor to an acid-palladium coupling reaction at a temperature sufficient for the diyne precursor to cyclize to form a polymer, wherein the diyne precursor has the following formula:
In the formula, R ¹ is independently selected from halogen, hydrogen, aliphatic, aryl, heteroaliphatic, or heteroaryl; each ^Ra is independently aryl; aliphatic, alkoxy, amide, amine, thioether, haloalkyl. , Nitro, halo, silyl, alicyclic, and aryl substituted with one or more functional groups selected from aryl; or alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, silyloxy, and hetero. Selected from electron donating groups selected from aryl ^{; R b} is the boron-containing part and
The polymer has the following formula
In the formula, R ¹ is independently selected from halogen, hydrogen, aliphatic, aryl, heteroaliphatic, or heteroaryl; each ^Ra is independently aryl; aliphatic, alkoxy, amide, amine, thioether, haloalkyl. , Nitro, halo, silyl, alicyclic, or aryl substituted with one or more functional groups selected from aryl; or alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, silyloxy, and hetero. A method selected from electron donating groups selected from aryls; each n is independently 1, 2, or 3; and m is in the range 1-1000. The method according to claim 12, wherein the boron-containing portion is boronic acid or B [-OC (R ⁶ ) ₂ C (R ⁶ ) ₂ O-], and each R ^{6 in the formula is independently aliphatic.} .. The method of claim 12 or 13, wherein the acid is selected from CF ₃ SO ₃ H, CH ₃ SO _{3 H, or a combination thereof.} The method according to any one of claims 12 to 14, wherein the temperature is in the range of −40 ° C. to ambient temperature. The method according to any one of claims 12 to 15, wherein the temperature is in the range of 0 ° C. to an ambient temperature. Further comprising the step of making the diyne precursor by halogen-metal exchange between a metal-containing compound containing Mg or Li and a compound having the following formula:
The method according to any one of claims 12 to 16, wherein Y is selected from Br, Cl, F, or I in the formula. The method of claim 17, wherein the metal-containing compound is selected from BuLi or t-BuLi.